U.S. patent number 6,762,152 [Application Number 10/009,981] was granted by the patent office on 2004-07-13 for substituted benzoyl ketones, methods for producing them and their use as herbicides.
This patent grant is currently assigned to Bayer Aktiengesellschaft. Invention is credited to Mark Wilhelm Drewes, Dieter Feucht, Stefan Lehr, Klaus-Helmut Muller, Rolf Pontzen, Otto Schallner, Hans-Georg Schwarz, Ingo Wetcholowsky, Heinz-Jurgen Wroblowsky.
United States Patent |
6,762,152 |
Muller , et al. |
July 13, 2004 |
Substituted benzoyl ketones, methods for producing them and their
use as herbicides
Abstract
The invention relates to novel substituted benzoyl ketones of
the formula (I) ##STR1## in which n represents 0, 1, 2 or 3, A
represents a single bond or represents alkanediyl (alkylene),
R.sup.1 represents hydrogen or represents in each case optionally
substituted alkyl or cycloalkyl, R.sup.2 represents hydrogen,
cyano, carbamoyl, halogen, or represents in each case optionally
substituted alkyl, alkoxy, alkoxycarbonyl, alkylthio,
alkylsulphinyl or alkylsulphonyl, R.sup.3 represents hydrogen,
nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, halogen, or
represents in each case optionally substituted alkyl, alkoxy,
alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino, dialkylamino
or dialkylaminosulphonyl, R.sup.4 represents nitro, cyano,
carboxyl, carbamoyl, thiocarbamoyl, halogen, or represents in each
case optionally substituted alkyl, alkoxy, alkylthio,
alkylsulphinyl, alkylsulphonyl, alkylamino, dialkyiamino or
dialkylaminosulphonyl, and Z represents an optionally substituted
4- to 12-membered, saturated or unsaturated, monocyclic or
bicyclic, heterocyclic grouping which, contains 1 to 4 hetero atoms
(up to 4 nitrogen atoms and optionally--alternatively or
additionally--one oxygen atom or one sulphur atom, or one SO
grouping or one SO.sub.2 grouping) and which additionally contains
one to three oxo g of the heterocycle roups (C.dbd.O) and/or thioxo
groups (C.dbd.S) as components, of the heterocycle, and to
processes for their preparation and to their use as herbicides.
Inventors: |
Muller; Klaus-Helmut
(Dusseldorf, DE), Lehr; Stefan (Langenfeld,
DE), Schallner; Otto (Monheim, DE),
Schwarz; Hans-Georg (Langenfeld, DE), Wroblowsky;
Heinz-Jurgen (Langenfeld, DE), Drewes; Mark
Wilhelm (Langenfeld, DE), Feucht; Dieter
(Monheim, DE), Pontzen; Rolf (Leichlingen,
DE), Wetcholowsky; Ingo (Estancia Marambaia,
BR) |
Assignee: |
Bayer Aktiengesellschaft
(Leverkusen, DE)
|
Family
ID: |
7907528 |
Appl.
No.: |
10/009,981 |
Filed: |
November 5, 2001 |
PCT
Filed: |
April 26, 2000 |
PCT No.: |
PCT/EP00/03712 |
PCT
Pub. No.: |
WO00/68204 |
PCT
Pub. Date: |
November 16, 2000 |
Foreign Application Priority Data
|
|
|
|
|
May 8, 1999 [DE] |
|
|
199 21 424 |
|
Current U.S.
Class: |
504/273; 514/384;
548/263.4; 548/263.2 |
Current CPC
Class: |
C07D
487/04 (20130101); C07D 249/12 (20130101); C07D
471/04 (20130101); C07D 275/06 (20130101); C07D
239/10 (20130101); C07D 285/13 (20130101); C07D
209/48 (20130101); C07D 233/70 (20130101); C07D
263/58 (20130101); C07D 213/64 (20130101); C07D
237/32 (20130101); C07D 253/04 (20130101); C07D
231/20 (20130101); A01N 43/653 (20130101); C07D
249/14 (20130101) |
Current International
Class: |
A01N
43/653 (20060101); A01N 43/64 (20060101); C07D
213/64 (20060101); C07D 285/13 (20060101); C07D
285/00 (20060101); C07D 231/20 (20060101); C07D
487/00 (20060101); C07D 209/48 (20060101); C07D
487/04 (20060101); C07D 209/00 (20060101); C07D
249/14 (20060101); C07D 471/04 (20060101); C07D
213/00 (20060101); C07D 237/00 (20060101); C07D
237/32 (20060101); C07D 239/00 (20060101); C07D
233/70 (20060101); C07D 233/00 (20060101); C07D
471/00 (20060101); C07D 231/00 (20060101); C07D
263/58 (20060101); C07D 275/06 (20060101); C07D
253/00 (20060101); C07D 253/04 (20060101); C07D
275/00 (20060101); C07D 249/12 (20060101); C07D
263/00 (20060101); C07D 239/10 (20060101); C07D
249/00 (20060101); C07D 249/12 (); C07D 285/12 ();
C07D 247/00 (); C07D 227/02 (); A01N 043/00 () |
Field of
Search: |
;548/263.2,263.4
;514/384 ;504/273 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
2102750 |
|
May 1994 |
|
CA |
|
2183641 |
|
Aug 1995 |
|
CA |
|
0 093 488 |
|
Nov 1983 |
|
EP |
|
0 617 026 |
|
Jul 1997 |
|
EP |
|
58-225070 |
|
Dec 1983 |
|
JP |
|
2-15069 |
|
Jan 1990 |
|
JP |
|
95/04716 |
|
Feb 1995 |
|
WO |
|
97/27187 |
|
Jul 1997 |
|
WO |
|
97/28122 |
|
Aug 1997 |
|
WO |
|
97/28136 |
|
Aug 1997 |
|
WO |
|
98/51153 |
|
Nov 1998 |
|
WO |
|
99/03856 |
|
Jan 1999 |
|
WO |
|
Other References
Hampel (Journal fuer praktische Chemie (Leipzig) (1969), 311(1),
78-81). Abstract.* .
Harris et al. (Journal of the American Chemical Society (1975),
97(11), 3270-1). Abstract.* .
Doub et al. (DE 2502119). Abstract.* .
Schaeffer et al. (FR 2654527). Abstract.* .
Djuric et al. (WO 92/21644). Abstract.* .
Von Deyn et al. (WO 96/26193). Abstract.* .
Von Deyn et al. (WO 96/26192). Abstract.* .
Go et al. (WO 97/27187). Abstract..
|
Primary Examiner: Kifle; Bruck
Attorney, Agent or Firm: Henderson; Richard E. L. Gil;
Joseph C.
Claims
What is claimed is:
1. A compound of formula (I) ##STR726##
or tautomers thereof, or a salt of a compound of formula (I) or
tautomers thereof, wherein n represents 0, 1, 2 or 3, A represents
a single bond or represents alkanediyl (alkylene) having 1 to 4
carbon atoms, R.sup.1 represents hydrogen, represents optionally
cyano, carboxyl, carbamoyl, halogen, C.sub.1 -C.sub.4 -alkoxy-,
C.sub.1 -C.sub.4 -alkylthio-, C.sub.1 -C.sub.4 -alkylsulphinyl- or
C.sub.1 -C.sub.4 -alkylsulphonyl-substituted alkyl having 1 to 6
carbon atoms, or represents optionally cyano-, carboxyl-,
carbamoyl-, halogen-, C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4
-alkoxy-carbonyl-substituted cycloalkyl having 3 to 6 carbon atoms,
R.sup.2 represents hydrogen, cyano, carbamoyl, halogen, represents
in each case optionally cyano-, carbamoyl-, halogen- or C.sub.1
-C.sub.4 -alkoxy-substituted alkyl, alkoxy or alkoxycarbonyl having
in each case up to 6 carbon atoms, or represents in each case
optionally halogen-substituted alkylthio, alkylsulphinyl or
alkylsulphonyl having in each case 1 to 6 carbon atoms, R.sup.3
represents hydrogen, nitro, cyano, carboxyl, carbamoyl,
thiocarbamoyl, halogen, represents in each case optionally
halogen-, C.sub.1 -C.sub.4 -alkoxy-, C.sub.1 -C.sub.4 -alkylthio-,
C.sub.1 -C.sub.4 -alkylsulphinyl- or C.sub.1 -C.sub.4
-alkylsulphonyl-substituted alkyl, alkoxy, alkylthio,
alkylsulphinyl or alkylsulphonyl having in each case up to 4 carbon
atoms in the alkyl groups, or represents alkylamino, dialkylamino
or dialkylaminosulphonyl having in each case up to 4 carbon atoms
in the alkyl groups, R.sup.4 represents nitro, cyano, carboxyl,
carbamoyl, thiocarbamoyl, halogen, represents in each case
optionally halogen-, C.sub.1 -C.sub.4 -alkoxy-, C.sub.1 -C.sub.4
-alkylthio-, C.sub.1 -C.sub.4 -alkylsulphinyl- or C.sub.1 -C.sub.4
-alkylsulphonyl-substituted alkyl, alkoxy, alkylthio,
alkylsulphinyl or alkylsuiphonyl having in each case up to 4 carbon
atoms in the alkyl groups, or represents alkylamino, dialkylamino
or dialkylaminosulphonyl having in each case up to 4 carbon atoms
in the alkyl groups, and Z represents one of the heterocyclic
groupings below ##STR727## ##STR728##
where the dotted line is in each case a single bond or a double
bond, Q represents oxygen or sulphur, R.sup.5 represents hydrogen,
hydroxyl, mercapto, cyano, halogen, represents in each case
optionally cyano-, halogen-, C.sub.1 -C.sub.4 -alkoxy-, C.sub.1
-C.sub.4 -alkylthio-, C.sub.1 -C.sub.4 -alkylsulphinyl- or C.sub.1
-C.sub.4 -alkylsulphonyl-substituted alkyl, alkylcarbonyl, alkoxy,
alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having
in each case up to 6 carbon atoms in the alkyl groups, represents
in each case optionally halogen-substituted alkylamino or
dialkylamino having in each case up to 6 carbon atoms in the alkyl
groups, represents in each case optionally halogen-substituted
alkenyl, alkinyl, alkenyloxy, alkenylthio or alkenylamino having in
each case up to 6 carbon atoms in the alkenyl- or alkinyl groups,
represents in each case optionally halogen-substituted cycloalkyl,
cycloalkyloxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyl,
cycloalkylalkoxy, cycloalkylalkylthio or cycloalkylalkylamino
having in each case 3 to 6 carbon atoms in the cycloalkyl groups
and optionally up to 4 carbon atoms in the alkyl moiety, or
represents in each case optionally halogen-, C.sub.1 -C.sub.4
-alkyl- or C.sub.1 -C.sub.4 -alkoxy-substituted phenyl, phenyloxy,
phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or
benzylamino, or--if two adjacent radicals R.sup.5 and R.sup.5 are
located at a double bond--together with the adjacent radical
R.sup.5 also represents a benzo grouping, and R.sup.6 represents
hydrogen, hydroxyl, amino, alkylideneamino having up to 4 carbon
atoms, represents in each case optionally halogen- or C.sub.1
-C.sub.4 -alkoxy-substituted alkyl, alkoxy, alkylamino,
dialkylamino or alkanoylamino having in each case up to 6 carbon
atoms in the alkyl groups, represents in each case optionally
halogen-substituted alkenyl, alkinyl or alkenyloxy having in each
case up to 6 carbon atoms in the alkenyl- or alkinyl groups,
represents in each case optionally halogen-substituted cycloalkyl,
cycloalkylalkyl or cycloalkylamino having in each case 3 to 6
carbon atoms in the cycloalkyl groups and optionally up to 3 carbon
atoms in the alkyl moiety, or represents in each case optionally
halogen-, C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4
-alkoxy-substituted phenyl or benzyl, or together with an adjacent
radical R.sup.5 or R.sup.6 represents optionally halogen- or
C.sub.1 -C.sub.4 -alkyl-substituted alkanediyl having 3 to 5 carbon
atoms,
where the individual radicals R.sup.5 and R.sup.6 --if a plurality
of them are attached to the same heterocyclic grouping--can have
identical or different meanings within the scope of the above
definition.
2. A compound according to claim 1, wherein A represents a single
bond, methylene, ethylidene (ethane-1,1-diyl) or dimethylene
(ethane-1,2-diyl), R.sup.1 represents hydrogen, represents in each
case optionally cyano-, carboxyl-, carbamoyl-, fluorine-,
chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-,
ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-,
n- or i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or
i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-,
i-, s- or t-butyl, or represents in each case optionally cyano-,
carboxyl-, carbamoyl-, fluorine-, chlorine-, methyl-, ethyl-,
methoxycarbonyl- or ethoxycarbonyl-substituted cyclopropyl,
cyclobutyl, cyclopentyl or cyclohexyl, R.sup.2 represents hydrogen,
cyano, carbamoyl, fluorine, chlorine, bromine, represents in each
case optionally cyano-, carbamoyl-, fluorine-, chlorine-, methoxy-
or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy,
ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or
i-propoxycarbonyl, or represents in each case optionally fluorine-
and/or chlorine-substituted methylthio, ethylthio, n- or
i-propylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, R.sup.3 represents hydrogen, nitro, cyano,
carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine,
iodine, represents in each case optionally fluorine- and/or
chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-,
ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-,
methylsulphonyl- or ethylsulphonyl-substituted methyl, ethyl, n- or
i-propyl, n-, i-, s- or t-butyl, represents in each case optionally
fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-substituted methoxy, ethoxy, n- or i-propoxy, represents
in each case optionally fluorine- and/or chlorine-substituted
methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,
ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl, or represents methylamino,
ethylamino, n- or i-propylamino, dimethylamino, diethylamino,
dimethylaminosulphonyl or diethylaminosulphonyl, R.sup.4 represents
nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine,
chlorine, bromine, represents in each case optionally fluorine-
and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-,
ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-,
methylsulphonyl- or ethylsulphonyl-substituted methyl, ethyl, n- or
i-propyl, n-, i-, s- or t-butyl, represents in each case optionally
fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-substituted methoxy, ethoxy, n- or i-propoxy, represents
in each case optionally fluorine- and/or chlorine-substituted
methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,
ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl, or represents methylamino,
ethylamino, n- or i-propylamino, dimethylamino, diethylamino,
dimethylaminosulphonyl or diethylaminosulphonyl, R.sup.5 represents
hydrogen, hydroxyl, mercapto, cyano, fluorine, chlorine, bromine,
iodine, represents in each case optionally fluorine-, chlorine-,
methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or t-butoxy-,
methylthio-, ethylthio-, n- or i-propylthio-, n-, i-, s- or
t-butylthio-, methylsulphinyl-, ethylsulphinyl-, n- or
i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or
i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-,
i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or
t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or
t-butylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, represents methylamino, ethylamino, n- or
i-propylamino, n-, i-, s- or t-butylamino, dimethylamino,
diethylamino, di-n-propylamino or di-i-propylamino, represents in
each case optionally fluorine- and/or chlorine-substituted ethenyl,
propenyl, butenyl, ethinyl, propinyl, butinyl, propenyloxy,
butenyloxy, propenylthio, butenylthio, propenylamino or
butenylamino, represents in each case optionally fluorine- and/or
chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,
cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio,
cyclohexylthio, cyclopropylamino, cyclobutylamino,
cyclopentylamino, cyclohexylamino, cyclopropylmethyl,
cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl,
cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy,
cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio,
cyclopentylmethylthio, cyclohexylmethylthio,
cyclopropylmethylamino, cyclobutylmethylamino,
cyclopentylmethylamino or cyclohexylmethylamino, or represents in
each case optionally fluorine-, chlorine-, methyl-, ethyl-, n- or
i-propyl-, n-, i-, s- or t-butyl-, methoxy-, ethoxy-, n- or
i-propoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino,
benzyl, benzyloxy, benzylthio or benzylamino, or--if two adjacent
radicals R.sup.5 and R.sup.5 are located at a double bond--together
with the adjacent radical R.sup.5 also represents a benzo grouping,
R.sup.6 represents hydrogen, hydroxyl, amino, represents in each
case optionally fluorine- and/or chlorine-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or
s-butyl, methoxy, ethoxy, n- or i-propoxy, methylamino, ethylamino
or dimethylamino, represents in each case optionally fluorine-
and/or chlorine-substituted ethenyl, propenyl, ethinyl, propinyl or
propenyloxy, represents in each case optionally fluorine- and/or
chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl
or cyclohexylmethyl, or represents in each case optionally
fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s-
or t-butyl-, methoxy-, ethoxy-, n- or i-propoxy-substituted phenyl
or benzyl, or together with an adjacent radical R.sup.5 or R.sup.6
represents in each case optionally methyl- and/or ethyl-substituted
propane-1,3-diyl (trimethylene), butane-1,4-diyl (tetramethylene)
or pentane-1,5-diyl (pentamethylene), and Z represents one of the
heterocyclic groupings below ##STR729##
3. A compound according to 1, wherein n represents 0 or 1, A
represents a single bond or represents methylene, R.sup.1
represents in each case optionally cyano-, fluorine-, chlorine-,
methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or
o-propylthio-, methylsulphinyl-, ethylsulphinyl-, n- or
i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or
i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, or
represents in each case optionally cyano-, fluorine-, chlorine-,
methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl
or cyclohexyl, R.sup.2 represents hydrogen, cyano, carbamoyl,
fluorine, chlorine, bromine, represents in each case optionally
cyano-, carbamoyl-, fluorine-, chlorine-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, or represents in
each case optionally fluorine- and/or chlorine-substituted
methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,
ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl, R.sup.3 represents
hydrogen, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl,
fluorine, chlorine, bromine, represents in each case optionally
fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-,
methylthio-, ethylthio-, n- or i-propylthio-, methylsulphinyl-,
ethylsulphinyl-, methylsulphonyl- or ethylsulphonyl-substituted
methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in
each case optionally fluorine- and/or chlorine-, methoxy-, ethoxy-,
n- or i-propoxy-substituted methoxy, ethoxy, n- or i-propoxy,
represents in each case optionally fluorine- and/or
chlorine-substituted methylthio, ethylthio, n- or i-propylthio,
methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl,
methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl, or
represents methylamino, ethylamino, n- or i-propylamino,
dimethylamino, diethylamino, dimethylaminosulphonyl or
diethylaminosulphonyl, R.sup.4 represents methylsulphonyl,
chlorine, methoxy, nitro, trifluoromethyl or methyl, R.sup.5
represents hydrogen, hydroxyl, chlorine, bromine, methyl, ethyl, n-
or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl,
trifluoromethyl, trichloromethyl, chlorodifluoromethyl,
fluorodichloromethyl, fluoroethyl, chloroethyl, difluoroethyl,
dichloroethyl, fluoro-n-propyl, fluoro-i-propyl, chloro-n-propyl,
chloro-i-propyl, methoxymethyl, ethoxymethyl, methoxyethyl,
ethoxyethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or
t-butoxy, fluoroethoxy, chloroethoxy, difluoroethoxy,
dichloroethoxy, trifluoroethoxy, trichloroethoxy,
chlorofluoroethoxy, chlorodifluoroethoxy, fluorodichloroethoxy,
methylthio, ethylthio, n- or i-propylthio, fluoroethylthio,
chloroethylthio, difluoroethylthio, dichloroethylthio,
chlorofluoroethylthio, chlorodifluoroethylthio,
fluorodichloroethylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, methylamino, dimethylamino, propenylthio,
butenylthio, propinylthio, butinylthio, cyclopropyl,
cyclopropylmethyl, cyclopropylmethoxy, phenyl or phenoxy, and
R.sup.6 represents amino, methyl, ethyl, n- or i-propyl, n-, i-, s-
or t-butyl, methoxy, ethoxy, methylamino, dimethylamino,
cyclopropyl or cyclopropylmethyl, or together with R.sup.5
represents propane-1,3-diyl (trimethylene), butane-1,4-diyl
(tetramethylene) or pentane-1,5-diyl (pentamethylene).
4. A compound according to claim 1, wherein R.sup.3 represents
hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl,
trifluoromethyl or methoxy, R.sup.5 represents hydrogen, bromine,
chlorine, methyl, ethyl, trifluoromethyl, cyclopropyl,
difluoroethyl, methylthio, ethylthio, methoxy, ethoxy, n- or
i-propoxy, trifluoroethoxy, methylamino or dimethylamino and
R.sup.6 represents hydrogen, amino, methyl, ethyl, methoxy, ethoxy,
cyclopropyl or dimethylamino.
5. A compound according to claim 1, wherein Q represents oxygen
(O).
6. A compound according to claim 1, wherein Z represents the
heterocyclic grouping ##STR730##
7. A compound according to claim 1, wherein R.sup.1 represents
cyclopropyl.
8. A compound according to claim 1, wherein R.sup.2 represents
hydrogen or cyano.
9. A compound according to claim 1, wherein R.sup.5 represents
bromine, methyl, ethyl, methoxy, methylthio, ethoxy,
methylsulphonyl or dimethylamino, and R.sup.6 represents amino,
methyl, ethyl, cyclopropyl, dimethylamino, methoxy or ethoxy.
10. A compound according to claim 1 of the formula (IA)
##STR731##
wherein n, A, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and Z are each as
defined in claim 1.
11. A compound according to claim 1 of the formula (IB),
##STR732##
wherein n, A, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and Z are each as
defined in claim 1.
12. A compound according to claim 1 of the formula (IC),
##STR733##
wherein n, A, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and Z are each as
defined in claim 1.
13. A process for preparing compounds according to claim 2,
comprising (a) reacting a ketone of the formula (II) ##STR734##
wherein R.sup.1 and R.sup.2 are each as defined in claim 2, with a
substituted benzoic acid of the formula (III) ##STR735## wherein n,
A, R.sup.3, R.sup.4 and Z are each as defined in claim 1, or (b)
isomerizing a benzoylisoxazole of the formula (IV) ##STR736##
wherein n, A, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and Z are each as
defined in claim 2, in the presence of one or more reaction
auxiliaries.
14. A herbicidal composition comprising a compound according to
claim 1 and an extender.
15. A method of controlling undesirable plants comprising applying
a compound according to claim 1 to undesirable plants and/or their
habitats.
16. A substituted benzoyl ketone according to claim 2, wherein Q
represents oxygen (O).
17. A sodium, potassium, magnesium, calcium, ammonium, C.sub.1
-C.sub.4 -alkyl-ammonium-, di(C.sub.1 -C.sup.4 -alkyl)ammonium,
tri(C.sub.1 -C.sub.4 -alkyl)ammonium, tetra(C.sub.1 -C.sub.4
-alkyl)ammonium, tri(C.sub.1 -C.sub.4 -alkyl)sulphonium, C.sub.5 -
or C.sub.6 -cycloalkyl-ammonium, or di(C.sub.1 -C.sub.2
-alkyl)benzylammonium salt of a compound of formula (I) according
to claim 1 or tautomers thereof.
Description
FIELD OF THE INVENTION
The invention relates to novel substituted benzoyl ketones, to
processes for their preparation and to their use as herbicides.
BACKGROUND OF THE INVENTION
It is already known that certain substituted benzoyl ketones have
herbicidal properties. (cf. EP-A-625505, EP-A-625508, U.S. Pat. No.
5,804,532, U.S. Pat. No. 5,846,906, WO-A-96/26193). However, the
activity of these compounds is not entirely satisfactory.
This invention, accordingly, provides the novel substituted benzoyl
ketones of the formula (I), ##STR2##
in which n represents 0, 1, 2 or 3, A represents a single bond or
represents alkanediyl (alkylene), R.sup.1 represents hydrogen or
represents in each case optionally substituted alkyl or cycloalkyl,
R.sup.2 represents hydrogen, cyano, carbamoyl, halogen, or
represents in each case optionally substituted alkyl, alkoxy,
alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl,
R.sup.3 represents hydrogen, nitro, cyano, carboxyl, carbamoyl,
thiocarbamoyl, halogen, or represents in each case optionally
substituted alkyl, alkoxy, alkylthio, alkylsulphinyl,
alkylsulphonyl, alkylamino, dialkylamino or dialkylaminosulphonyl,
R.sup.4 represents nitro, cyano, carboxyl, carbamoyl,
thiocarbamoyl, halogen, or represents in each case optionally
substituted alkyl, alkoxy, alkylthio, alkylsulphinyl,
alkylsulphonyl, alkylamino, dialkylamino or dialkylaminosulphonyl,
and
DETAILED DESCRIPTION Z represents an optionally substituted 4- to
12-membered, saturated or unsaturated, monocyclic or bicyclic,
heterocyclic grouping which contains 1 to 4 hetero atoms (up to 4
nitrogen atoms and optionally--alternatively or additionally--one
oxygen atom or one sulphur atom, or one SO grouping or one SO.sub.2
grouping) and which additionally contains one to three oxo groups
(C.dbd.O) and/or thioxo groups (C.dbd.S) as components of the
heterocycle,
including all possible tautomeric forms of the compounds of the
general formula (I) and the possible salts of the compounds of the
general formula (I).
In the definitions, the hydrocarbon chains, such as alkyl or
alkanediyl, are in each case straight-chain or branched--including
in combination with heteroatoms, such as in alkoxy. n preferably
represents 0, 1 or 2. A preferably represents a single bond or
represents alkanediyl (alkylene) having 1 to 4 carbon atoms.
R.sup.1 preferably represents hydrogen, represents optionally
cyano, carboxyl, carbamoyl, halogen, C.sub.1 -C.sub.4 -alkoxy-,
C.sub.1 -C.sub.4 -alkylthio-, C.sub.1 -C.sub.4 -alkylsulphinyl- or
C.sub.1 -C.sub.4 -alkylsulphonyl-substituted alkyl having 1 to 6
carbon atoms, or represents optionally cyano-, carboxyl-,
carbamoyl-, halogen-, C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4
-alkoxy-carbonyl-substituted cycloalkyl having 3 to 6 carbon atoms.
R.sup.2 preferably represents hydrogen, cyano, carbamoyl, halogen,
represents in each case optionally cyano-, carbamoyl-, halogen- or
C.sub.1 -C.sub.4 -alkoxy-substituted alkyl, alkoxy or
alkoxycarbonyl having in each case up to 6 carbon atoms, or
represents in each case optionally halogen-substituted alkylthio,
alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon
atoms. R.sup.3 preferably represents hydrogen, nitro, cyano,
carboxyl, carbamoyl, thiocarbamoyl, halogen, represents in each
case optionally halogen-, C.sub.1 -C.sub.4 -alkoxy-, C.sub.1
-C.sub.4 -alkylthio-, C.sub.1 -C.sub.4 -alkylsulphinyl- or C.sub.1
-C.sub.4 -alkylsulphonyl-substituted alkyl, alkoxy, alkylthio,
alkylsulphinyl or alkylsulphonyl having in each case up to 4 carbon
atoms in the alkyl groups, or represents alkylamino, dialkylamino
or dialkylaminosulphonyl having in each case up to 4 carbon atoms
in the alkyl groups. R.sup.4 preferably represents nitro, cyano,
carboxyl, carbamoyl, thiocarbamoyl, halogen, represents in each
case optionally halogen-, C.sub.1 -C.sub.4 -alkoxy-, C.sub.1
-C.sub.4 -alkylthio-, C.sub.1 -C.sub.4 -alkylsulphinyl- or C.sub.1
-C.sub.4 -alkylsulphonyl-substituted alkyl, alkoxy, alkylthio,
alkylsulphinyl or alkylsulphonyl having in each case up to 4 carbon
atoms in the alkyl groups, or represents alkylamino, dialkylamino
or dialkylaminosulphonyl having in each case up to 4 carbon atoms
in the alkyl groups. Z preferably represents one of the
heterocyclic groupings below ##STR3## ##STR4##
where the dotted line is in each case a single bond or a double
bond, and each heterocyclic grouping preferably only carries two
substituents of the definition R.sup.5 and/or R.sup.6, Q represents
oxygen or sulphur, R.sup.5 represents hydrogen, hydroxyl, mercapto,
cyano, halogen, represents in each case optionally cyano-,
halogen-, C.sub.1 -C.sub.4 -alkoxy-, C.sub.1 -C.sub.4 -alkylthio-,
C.sub.1 -C.sub.4 -alkylsulphinyl- or C.sub.1 -C.sub.4
-alkylsulphonyl-substituted alkyl, alkylcarbonyl, alkoxy,
alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having
in each case up to 6 carbon atoms in the alkyl groups, represents
in each case optionally halogen-substituted alkylamino or
dialkylamino having in each case up to 6 carbon atoms in the alkyl
groups, represents in each case optionally halogen-substituted
alkenyl, alkinyl, alkenyloxy, alkenylthio or alkenylamino having in
each case up to 6 carbon atoms in the alkenyl- or alkinyl groups,
represents in each case optionally halogen-substituted cycloalkyl,
cycloalkyloxy, cycloalkylthio, cycloalkylamino, cycloalkylalkyl,
cycloalkylalkoxy, cycloalkylalkylthio or cycloalkylalkylamino
having in each case 3 to 6 carbon atoms in the cycloalkyl groups
and optionally up to 4 carbon atoms in the alkyl moiety, or
represents in each case optionally halogen-, C.sub.1 -C.sub.4
-alkyl- or C.sub.1 -C.sub.4 -alkoxy-substituted phenyl, phenyloxy,
phenylthio, phenylamino, benzyl, benzyloxy, benzylthio or
benzylamino, or--if two adjacent radicals R.sup.5 and R.sup.5 are
located at a double bond--together with the adjacent radical
R.sup.5 also represents a benzo grouping, and R.sup.6 represents
hydrogen, hydroxyl, amino, alkylideneamino having up to 4 carbon
atoms, represents in each case optionally halogen- or C.sub.1
-C.sub.4 -alkoxy-substituted alkyl, alkoxy, alkylamino,
dialkylamino or alkanoylamino having in each case up to 6 carbon
atoms in the alkyl groups, represents in each case optionally
halogen-substituted alkenyl, alkinyl or alkenyloxy having in each
case up to 6 carbon atoms in the alkenyl- or alkinyl groups,
represents in each case optionally halogen-substituted cycloalkyl,
cycloalkylalkyl or cycloalkylamino having in each case 3 to 6
carbon atoms in the cycloalkyl groups and optionally up to 3 carbon
atoms in the alkyl moiety, or represents in each case optionally
halogen-, C.sub.1 -C.sub.4 -alkyl- or C.sub.1 -C.sub.4
-alkoxy-substituted phenyl or benzyl, or together with an adjacent
radical R.sup.5 or R.sup.6 represents optionally halogen- or
C.sub.1 -C.sub.4 -alkyl-substituted alkanediyl having 3 to 5 carbon
atoms,
where the individual radicals R.sup.5 and R.sup.6 --if a plurality
of them are attached to the same heterocyclic grouping--can have
identical or different meanings within the scope of the above
definition. Q preferably represents oxygen. R.sup.5 preferably
represents hydrogen, hydroxyl, mercapto, cyano, fluorine, chlorine,
bromine, iodine, represents in each case optionally fluorine-,
chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, n-, i-, s- or
t-butoxy-, methylthio-, ethylthio-, n- or i-propylthio-, n-, i-, s-
or t-butylthio-, methylsulphinyl-, ethylsulphinyl-, n- or
i-propylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, n- or
i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-,
i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or
t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or
t-butylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, represents methylamino, ethylamino, n- or
i-propylamino, n-, i-, s- or t-butylamino, dimethylamino,
diethylamino, di-n-propylamino or di-i-propylamino, represents in
each case optionally fluorine- and/or chlorine-substituted ethenyl,
propenyl, butenyl, ethinyl, propinyl, butinyl, propenyloxy,
butenyloxy, propenylthio, butenylthio, propenylamino or
butenylamino, represents in each case optionally fluorine- and/or
chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy,
cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio,
cyclohexylthio, cyclopropylamino, cyclobutylamino,
cyclopentylamino, cyclohexylamino, cyclopropylmethyl,
cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl,
cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy,
cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio,
cyclopentylmethylthio, cyclohexylmethylthio,
cyclopropylmethylamino, cyclobutylmethylamino,
cyclopentylmethylamino or cyclohexylmethylamino, or represents in
each case optionally fluorine-, chlorine-, methyl-, ethyl-, n- or
i-propyl-, n-, i-, s- or t-butyl-, methoxy-, ethoxy-, n- or
i-propoxy-substituted phenyl, phenyloxy, phenylthio, phenylamino,
benzyl, benzyloxy, benzylthio or benzylamino, or--if two adjacent
radicals R.sup.5 and R.sup.5 are located at a double bond--together
with the adjacent radical R.sup.5 also represents a benzo grouping.
R.sup.6 preferably represents hydrogen, hydroxyl, amino, represents
in each case optionally fluorine- and/or chlorine-, methoxy- or
ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or
s-butyl, methoxy, ethoxy, n- or i-propoxy, methylamino, ethylamino
or dimethylamino, represents in each case optionally fluorine-
and/or chlorine-substituted ethenyl, propenyl, ethinyl, propinyl or
propenyloxy, represents in each case optionally fluorine- and/or
chlorine-substituted cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl
or cyclohexylmethyl, or represents in each case optionally
fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s-
or t-butyl-, methoxy-, ethoxy-, n- or i-propoxy-substituted phenyl
or benzyl, or together with an adjacent radical R.sup.5 or R.sup.6
represents in each case optionally methyl- and/or ethyl-substituted
propane-1,3-diyl (trimethylene), butane-1,4-diyl (tetramethylene)
or pentane-1,5-diyl (pentamethylene). n particularly preferably
represents 0 or 1. A particularly preferably represents a single
bond, methylene, ethylidene (ethane-1,1-diyl) or dimethylene
(ethane-1,2-diyl). R.sup.1 particularly preferably represents
hydrogen, represents in each case optionally cyano-, carboxyl-,
carbamoyl-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-, methylthio-, ethylthio-, n- or i-propylthio-,
methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-,
methylsulphonyl-, ethylsulphonyl-, n- or
i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-,
i-, s- or t-butyl, or represents in each case optionally cyano-,
carboxyl-, carbamoyl-, fluorine-, chlorine-, methyl-, ethyl-,
methoxycarbonyl- or ethoxycarbonyl-substituted cyclopropyl,
cyclobutyl, cyclopentyl or cyclohexyl. R.sup.2 particularly
preferably represents hydrogen, cyano, carbamoyl, fluorine,
chlorine, bromine, represents in each case optionally cyano-,
carbamoyl-, fluorine-, chlorine-, methoxy- or ethoxy-substituted
methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy,
methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, or
represents in each case optionally fluorine- and/or
chlorine-substituted methylthio, ethylthio, n- or i-propylthio,
methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl,
methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl. R.sup.3
particularly preferably represents hydrogen, nitro, cyano,
carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine,
iodine, represents in each case optionally fluorine- and/or
chlorine-, methoxy-, ethoxy-, n- or i-propoxy-, methylthio-,
ethylthio-, n- or i-propylthio-, methylsulphinyl-, ethylsulphinyl-,
methylsulphonyl- or ethylsulphonyl-substituted methyl, ethyl, n- or
i-propyl, n-, i-, s- or t-butyl, represents in each case optionally
fluorine- and/or chlorine-, methoxy-, ethoxy-, n- or
i-propoxy-substituted methoxy, ethoxy, n- or i-propoxy, represents
in each case optionally fluorine- and/or chlorine-substituted
methylthio, ethylthio, n- or i-propylthio, methylsulphinyl,
ethylsulphinyl, n- or i-propylsulphinyl, methylsulphonyl,
ethylsulphonyl, n- or i-propylsulphonyl, or represents methylamino,
ethylamino, n- or i-propylamino, dimethylamino, diethylamino,
dimethylaminosulphonyl or diethylaminosulphonyl. R.sup.4
particularly preferably represents nitro, cyano, carboxyl,
carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, represents
in each case optionally fluorine- and/or chlorine-, methoxy-,
ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or
i-propylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl-
or ethylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-,
i-, s- or t-butyl, represents in each case optionally fluorine-
and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted
methoxy, ethoxy, n- or i-propoxy, represents in each case
optionally fluorine- and/or chlorine-substituted methylthio,
ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n-
or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, or represents methylamino, ethylamino, n- or
i-propylamino, dimethylamino, diethylamino, dimethylaminosulphonyl
or diethylaminosulphonyl. R.sup.5 particularly preferably
represents hydrogen, hydroxyl, chlorine, bromine, methyl, ethyl, n-
or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl,
trifluoromethyl, trichloromethyl, chlorodifluoromethyl,
fluorodichloromethyl, fluoroethyl, chloroethyl, difluoroethyl,
dichloroethyl, fluoro-n-propyl, fluoro-i-propyl, chloro-n-propyl,
chloro-i-propyl, methoxymethyl, ethoxymethyl, methoxyethyl,
ethoxyethyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or
t-butoxy, fluoroethoxy, chloroethoxy, difluoroethoxy,
dichloroethoxy, trifluoroethoxy, trichloroethoxy,
chlorofluoroethoxy, chlorodifluoroethoxy, fluorodichloroethoxy,
methylthio, ethylthio, n- or i-propylthio, fluoroethylthio,
chloroethylthio, difluoroethylthio, dichloroethylthio,
chlorofluoroethylthio, chlorodifluoroethylthio,
fluorodichloroethylthio, methylsulphinyl, ethylsulphinyl, n- or
i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, methylamino, dimethylamino, propenylthio,
butenylthio, propinylthio, butinylthio, cyclopropyl,
cyclopropylmethyl, cyclopropylmethoxy, phenyl or phenoxy. R.sup.6
particularly preferably represents amino, methyl, ethyl, n- or
i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylamino,
dimethylamino, cyclopropyl or cyclopropylmethyl, or together with
R.sup.5 represents propane-1,3-diyl (trimethylene), butane-1,4-diyl
(tetramethylene) or pentane-1,5-diyl (pentamethylene). Z
particularly preferably represents the groupings below ##STR5##
where Q, R.sup.5 and R.sup.6 are each as defined above. A very
particularly preferably represents a single bond or represents
methylene. R.sup.1 very particularly preferably represents in each
case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n-
or i-propoxy-, methylthio-, ethylthio-, n- or o-propylthio-,
methylsulphinyl-, ethylsulphinyl-, n- or i-propylsulphinyl-,
methylsulphonyl-, ethylsulphonyl-, n- or
i-propylsulphonyl-substituted methyl, ethyl, n- or i-propyl, or
represents in each case optionally cyano-, fluorine-, chlorine-,
methyl- or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl
or cyclohexyl. R.sup.2 very particularly preferably represents
hydrogen, cyano, carbamoyl, fluorine, chlorine, bromine, represents
in each case optionally cyano-, carbamoyl-, fluorine-, chlorine-,
methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, or
represents in each case optionally fluorine- and/or
chlorine-substituted methylthio, ethylthio, n- or i-propylthio,
methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl,
methylsulphonyl, ethylsulphonyl, n- or i-propylsulphonyl. R.sup.3
very particularly preferably represents hydrogen, nitro, cyano,
carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine,
represents in each case optionally fluorine- and/or chlorine-,
methoxy-, ethoxy-, n- or i-propoxy-, methylthio-, ethylthio-, n- or
i-propylthio-, methylsulphinyl-, ethylsulphinyl-, methylsulphonyl-
or ethylsulphonyl-substituted methyl, ethyl, n- or i-propyl, n-,
i-, s- or t-butyl, represents in each case optionally fluorine-
and/or chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted
methoxy, ethoxy, n- or i-propoxy, represents in each case
optionally fluorine- and/or chlorine-substituted methylthio,
ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, n-
or i-propylsulphinyl, methylsulphonyl, ethylsulphonyl, n- or
i-propylsulphonyl, or represents methylamino, ethylamino, n- or
i-propylamnino, dimethylamino, diethylamino, dimethylaminosulphonyl
or diethylaminosulphonyl. R.sup.4 very particularly preferably
represents methylsulphonyl, chlorine, methoxy, nitro,
trifluoromethyl or methyl. R.sup.5 very particularly preferably
represents hydrogen, bromine, chlorine, methyl, ethyl,
trifluoromethyl, cyclopropyl, difluoroethyl, methylthio, ethylthio,
methoxy, ethoxy, n- or i-propoxy, trifluoroethoxy, methylamino or
dimethylamino. R.sup.6 very particularly preferably represents
hydrogen, amino, methyl, ethyl, cyclopropyl, dimethylamino methoxy
or ethoxy. R.sup.1 most preferably represents cyclopropyl. R.sup.2
most preferably represents hydrogen or cyano. R.sup.3 most
preferably represents hydrogen, nitro, cyano, fluorine, chlorine,
bromine, methyl, trifluoromethyl or methoxy. R.sup.5 most
preferably represents bromine, methyl, ethyl, methoxy, methylthio,
ethoxy, methylsulfonyl or dimethylamino. R.sup.6 most preferably
represents amino, methyl, ethyl, cyclopropyl, dimethylamino,
methoxy or ethoxy.
Preference according to the invention is given to the compounds of
the formula (I) which contain a combination of the meanings given
above as being preferred.
Particular preference according to the invention is given to the
compounds of the formula (I) which contain a combination of the
meanings given above as being particularly preferred.
Very particular preference according to the invention is given to
the compounds of the formula (I) which contain a combination of the
meanings given above as being very particularly preferred.
Most preference according to the invention is given to the
compounds of the formula (I) which contain a combination of the
meanings given above as being most preferred.
Part of the subject-matter of the present invention are in
particular the compounds of the formulae (IA), (IB) and (IC):
##STR6##
in which Z represents the groupings below ##STR7##
and n, A, Q, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and
R.sup.6 are each as defined above.
The abovementioned general or preferred radical definitions apply
both to the end products of the formula (I) and, correspondingly,
to the starting materials or intermediates required in each case
for the preparation. These radical definitions can be combined with
one another as desired, i.e. including combinations between the
given preferred ranges.
Examples of the compounds of the general formula (I) according to
the invention are listed in the groups below.
Group 1
##STR8##
R.sup.3, (R.sup.4).sub.n, R.sup.5 and R.sup.6 have example, the
meaning given in the table below:
(position-) R.sup.3 (R.sup.4).sub.n R.sup.5 R.sup.6 H -- CF.sub.3
CH.sub.3 F -- CF.sub.3 CH.sub.3 Cl -- CF.sub.3 CH.sub.3 Br --
CF.sub.3 CH.sub.3 I -- CF.sub.3 CH.sub.3 NO.sub.2 -- CF.sub.3
CH.sub.3 CN -- CF.sub.3 CH.sub.3 CH.sub.3 -- CF.sub.3 CH.sub.3
OCH.sub.3 -- CF.sub.3 CH.sub.3 CF.sub.3 -- CF.sub.3 CH.sub.3
OCHF.sub.2 -- CF.sub.3 CH.sub.3 OCF.sub.3 -- CF.sub.3 CH.sub.3
SO.sub.2 CH.sub.3 -- CF.sub.3 CH.sub.3 H -- OCH.sub.3 CH.sub.3 F --
OCH.sub.3 CH.sub.3 Cl -- OCH.sub.3 CH.sub.3 Br -- OCH.sub.3
CH.sub.3 I -- OCH.sub.3 CH.sub.3 NO.sub.2 -- OCH.sub.3 CH.sub.3 CN
-- OCH.sub.3 CH.sub.3 CH.sub.3 -- OCH.sub.3 CH.sub.3 OCH.sub.3 --
OCH.sub.3 CH.sub.3 CF.sub.3 -- OCH.sub.3 CH.sub.3 OCHF.sub.2 --
OCH.sub.3 CH.sub.3 OCF.sub.3 -- OCH.sub.3 CH.sub.3 SO.sub.2
CH.sub.3 -- OCH.sub.3 CH.sub.3 H -- SCH.sub.3 CH.sub.3 F --
SCH.sub.3 CH.sub.3 Cl -- SCH.sub.3 CH.sub.3 Br -- SCH.sub.3
CH.sub.3 CN -- N(CH.sub.3).sub.2 CH.sub.3 CH.sub.3 --
N(CH.sub.3).sub.2 CH.sub.3 OCH.sub.3 -- N(CH.sub.3).sub.2 CH.sub.3
CF.sub.3 -- N(CH.sub.3).sub.2 CH.sub.3 OCHF.sub.2 --
N(CH.sub.3).sub.2 CH.sub.3 OCF.sub.3 -- N(CH.sub.3).sub.2 CH.sub.3
SO.sub.2 CH.sub.3 -- N(CH.sub.3).sub.2 CH.sub.3 H -- OCH.sub.3
##STR9## F -- OCH.sub.3 ##STR10## Cl -- OCH.sub.3 ##STR11## Br --
OCH.sub.3 ##STR12## I -- OCH.sub.3 ##STR13## NO.sub.2 -- OCH.sub.3
##STR14## CN -- OCH.sub.3 ##STR15## CH.sub.3 -- OCH.sub.3 ##STR16##
OCH.sub.3 -- OCH.sub.3 ##STR17## CF.sub.3 -- OCH.sub.3 ##STR18## I
-- SCH.sub.3 CH.sub.3 NO.sub.2 -- SCH.sub.3 CH.sub.3 CN --
SCH.sub.3 CH.sub.3 CH.sub.3 -- SCH.sub.3 CH.sub.3 OCH.sub.3 --
SCH.sub.3 CH.sub.3 CF.sub.3 -- SCH.sub.3 CH.sub.3 OCHF.sub.2 --
SCH.sub.3 CH.sub.3 OCF.sub.3 -- SCH.sub.3 CH.sub.3 SO.sub.2
CH.sub.3 -- SCH.sub.3 CH.sub.3 H -- OC.sub.2 H.sub.5 CH.sub.3 F --
OC.sub.2 H.sub.5 CH.sub.3 Cl -- OC.sub.2 H.sub.5 CH.sub.3 Br --
OC.sub.2 H.sub.5 CH.sub.3 I -- OC.sub.2 H.sub.5 CH.sub.3 NO.sub.2
-- OC.sub.2 H.sub.5 CH.sub.3 CN -- OC.sub.2 H.sub.5 CH.sub.3
CH.sub.3 -- OC.sub.2 H.sub.5 CH.sub.3 OCH.sub.3 -- OC.sub.2 H.sub.5
CH.sub.3 CF.sub.3 -- OC.sub.2 H.sub.5 CH.sub.3 OCHF.sub.2 --
OC.sub.2 H.sub.5 CH.sub.3 OCF.sub.3 -- OC.sub.2 H.sub.5 CH.sub.3
SO.sub.2 CH.sub.3 -- OC.sub.2 H.sub.5 CH.sub.3 H --
N(CH.sub.3).sub.2 CH.sub.3 F -- N(CH.sub.3).sub.2 CH.sub.3 Cl --
N(CH.sub.3).sub.2 CH.sub.3 Br -- N(CH.sub.3).sub.2 CH.sub.3 I --
N(CH.sub.3).sub.2 CH.sub.3 NO.sub.2 -- N(CH.sub.3).sub.2 CH.sub.3
OCHF.sub.2 -- OCH.sub.3 ##STR19## OCF.sub.3 -- OCH.sub.3 ##STR20##
SO.sub.2 CH.sub.3 -- OCH.sub.3 ##STR21## H (3-) Cl CF.sub.3
CH.sub.3 F (3-) Cl CH.sub.3 CH.sub.3 Cl (3-) Cl OCH.sub.3 CH.sub.3
Br (3-) Cl Br ##STR22## Cl (3-) Cl CF.sub.3 CH.sub.3 NO.sub.2 (3-)
Cl CH.sub.3 CH.sub.3 Cl (3-) Cl SCH.sub.3 CH.sub.3 CH.sub.3 (3-) Cl
Cl CH.sub.3 OCH.sub.3 (3-) Cl OCH.sub.3 CH.sub.3 CF.sub.3 (3-) Cl
CF.sub.3 CH.sub.3 OCHF.sub.2 (3-) Cl CH.sub.3 CH.sub.3 OCF.sub.3
(3-) Cl CH.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (3-) Cl OCH.sub.3
CH.sub.3
Group 2
##STR23##
R.sup.3, (R.sup.4).sub.n, R.sup.5 and R.sup.6 have, for example,
the meanings given in the table below:
(position-) R.sup.3 (R.sup.4).sub.n R.sup.5 R.sup.6 Cl (2-) Cl
CF.sub.3 CH.sub.3 Cl (2-) Cl SCH.sub.3 CH.sub.3 Cl (2-) Cl SC.sub.2
H.sub.5 CH.sub.3 Cl (2-) Cl SC.sub.3 H.sub.7 CH.sub.3 Cl (2-) Cl
SC.sub.3 H.sub.7 -i CH.sub.3 Cl (2-) Cl ##STR24## CH.sub.3 Cl (2-)
Cl ##STR25## CH.sub.3 Cl (2-) Cl ##STR26## CH.sub.3 Cl (2-) Cl
##STR27## CH.sub.3 Cl (2-) Cl ##STR28## CH.sub.3 Cl (2-) Cl
SCH.dbd.C.dbd.CH.sub.2 CH.sub.3 Cl (2-) Cl SCH.sub.2 CN CH.sub.3 Cl
(2-) Cl SCH.sub.2 CH.sub.2 CN CH.sub.3 Cl (2-) Cl OCH.sub.3
CH.sub.3 Cl (2-) Cl OC.sub.2 H.sub.5 CH.sub.3 Cl (2-) Cl OC.sub.3
H.sub.7 CH.sub.3 Cl (2-) Cl OC.sub.3 H.sub.7 -i CH.sub.3 Cl (2-) Cl
OC.sub.4 H.sub.9 CH.sub.3 Cl (2-) Cl OCH.sub.2 CF.sub.3 CH.sub.3 Cl
(2-) Cl ##STR29## CH.sub.3 Cl (2-) Cl OC.sub.6 H.sub.5 CH.sub.3 Cl
(2-) Cl H CH.sub.3 Cl (2-) Cl CH.sub.3 CH.sub.3 Cl (2-) Cl C.sub.2
H.sub.5 CH.sub.3 Cl (2-) Cl C.sub.3 H.sub.7 CH.sub.3 Cl (2-) Cl
C.sub.3 H.sub.7 -i CH.sub.3 Cl (2-) Cl C.sub.4 H.sub.9 CH.sub.3 Cl
(2-) Cl C.sub.4 H.sub.9 -i CH.sub.3 Cl (2-) Cl C.sub.4 H.sub.9 -s
CH.sub.3 Cl (2-) Cl C.sub.4 H.sub.9 -t CH.sub.3 Cl (2-) Cl
##STR30## CH.sub.3 Cl (2-) Cl ##STR31## CH.sub.3 Cl (2-) Cl
CH.dbd.CHCH.sub.3 CH.sub.3 Cl (2-) Cl ##STR32## CH.sub.3 Cl (2-) Cl
##STR33## CH.sub.3 Cl (2-) Cl ##STR34## CH.sub.3 Cl (2-) Cl
N(CH.sub.3).sub.2 CH.sub.3 Cl (2-) Cl ##STR35## CH.sub.3 Cl (2-) Cl
Cl CH.sub.3 Cl (2-) Cl Br CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl
CF.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl SCH.sub.3 CH.sub.3
SO.sub.2 CH.sub.3 (2-) Cl SC.sub.2 H.sub.5 CH.sub.3 SO.sub.2
CH.sub.3 (2-) Cl SC.sub.3 H.sub.7 CH.sub.3 SO.sub.2 CH.sub.3 (2-)
Cl SC.sub.3 H.sub.7 -i CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl ##STR36##
CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl ##STR37## CH.sub.3 SO.sub.2
CH.sub.3 (2-) Cl ##STR38## CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl
##STR39## CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl ##STR40## CH.sub.3
SO.sub.2 CH.sub.3 (2-) Cl SCH.dbd.C.dbd.CH.sub.2 CH.sub.3 SO.sub.2
CH.sub.3 (2-) Cl SCH.sub.2 CN CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl
SCH.sub.2 CH.sub.2 CN CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl OCH.sub.3
CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl OC.sub.2 H.sub.5 CH.sub.3
SO.sub.2 CH.sub.3 (2-) Cl OC.sub.3 H.sub.7 CH.sub.3 SO.sub.2
CH.sub.3 (2-) Cl OC.sub.3 H.sub.7 -i CH.sub.3 SO.sub.2 CH.sub.3
(2-) Cl OC.sub.4 H.sub.9 CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl
OCH.sub.2 CF.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl ##STR41##
CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl OC.sub.6 H.sub.5 CH.sub.3
SO.sub.2 CH.sub.3 (2-) Cl H CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl
CH.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl C.sub.2 H.sub.5
CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl C.sub.3 H.sub.7 CH.sub.3
SO.sub.2 CH.sub.3 (2-) Cl C.sub.3 H.sub.7 -i CH.sub.3 SO.sub.2
CH.sub.3 (2-) Cl C.sub.4 H.sub.9 CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl
C.sub.4 H.sub.9 -i CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl C.sub.4
H.sub.9 -s CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl C.sub.4 H.sub.9 -t
CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl ##STR42## CH.sub.3 SO.sub.2
CH.sub.3 (2-) Cl ##STR43## CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl
CH.dbd.CHCH.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl ##STR44##
CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl ##STR45## CH.sub.3 SO.sub.2
CH.sub.3 (2-) Cl ##STR46## CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl
N(CH.sub.3).sub.2 CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl ##STR47##
CH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl Cl CH.sub.3 SO.sub.2 CH.sub.3
(2-) Cl Br CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 CF.sub.3 CH.sub.3 Cl
(2-) SO.sub.2 CH.sub.3 SCH.sub.3 CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3
SC.sub.2 H.sub.5 CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 SC.sub.3
H.sub.7 CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 SC.sub.3 H.sub.7 -i
CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 ##STR48## CH.sub.3 Cl (2-)
SO.sub.2 CH.sub.3 ##STR49## CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3
##STR50## CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 ##STR51## CH.sub.3 Cl
(2-) SO.sub.2 CH.sub.3 ##STR52## CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3
SCH.dbd.C.dbd.CH.sub.2 CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 SCH.sub.2
CN CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 SCH.sub.2 CH.sub.2 CN
CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 OCH.sub.3 CH.sub.3 Cl (2-)
SO.sub.2 CH.sub.3 OC.sub.2 H.sub.5 CH.sub.3 Cl (2-) SO.sub.2
CH.sub.3 OC.sub.3 H.sub.7 CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3
OC.sub.3 H.sub.7 -i CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 OC.sub.4
H.sub.9 CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 OCH.sub.2 CF.sub.3
CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 ##STR53## CH.sub.3 Cl (2-)
SO.sub.2 CH.sub.3 OC.sub.6 H.sub.5 CH.sub.3 Cl (2-) SO.sub.2
CH.sub.3 H CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 Cl
(2-) SO.sub.2 CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 Cl (2-) SO.sub.2
CH.sub.3 C.sub.3 H.sub.7 CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 C.sub.3
H.sub.7 -i CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 C.sub.4 H.sub.9
CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 C.sub.4 H.sub.9 -i CH.sub.3 Cl
(2-) SO.sub.2 CH.sub.3 C.sub.4 H.sub.9 -s CH.sub.3 Cl (2-) SO.sub.2
CH.sub.3 C.sub.4 H.sub.9 -t CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3
##STR54## CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 ##STR55## CH.sub.3 Cl
(2-) SO.sub.2 CH.sub.3 CH.dbd.CHCH.sub.3 CH.sub.3 Cl (2-) SO.sub.2
CH.sub.3 ##STR56## CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 ##STR57##
CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 ##STR58## CH.sub.3 Cl (2-)
SO.sub.2 CH.sub.3 N(CH.sub.3).sub.2 CH.sub.3 Cl (2-) SO.sub.2
CH.sub.3 ##STR59## CH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 Cl CH.sub.3
Cl (2-) SO.sub.2 CH.sub.3 Br CH.sub.3 Cl (2-) Cl CF.sub.3 ##STR60##
Cl (2-) Cl SCH.sub.3 ##STR61## Cl (2-) Cl SC.sub.2 H.sub.5
##STR62## Cl (2-) Cl SC.sub.3 H.sub.7 ##STR63## Cl (2-) Cl SC.sub.3
H.sub.7 -i ##STR64## Cl (2-) Cl ##STR65## ##STR66## Cl (2-) Cl
##STR67## ##STR68## Cl (2-) Cl ##STR69## ##STR70## Cl (2-) Cl
##STR71## ##STR72## Cl (2-) Cl ##STR73## ##STR74## Cl (2-) Cl
SCH.dbd.C.dbd.CH.sub.2 ##STR75## Cl (2-) Cl SCH.sub.2 CN ##STR76##
Cl (2-) Cl SCH.sub.2 CH.sub.2 CN ##STR77## Cl (2-) Cl OCH.sub.3
##STR78## Cl (2-) Cl OC.sub.2 H.sub.5 ##STR79## Cl (2-) Cl OC.sub.3
H.sub.7 ##STR80## Cl (2-) Cl OC.sub.3 H.sub.7 -i ##STR81## Cl (2-)
Cl OC.sub.4 H.sub.9 ##STR82## Cl (2-) Cl OCH.sub.2 CF.sub.3
##STR83## Cl (2-) Cl ##STR84## ##STR85## Cl (2-) Cl OC.sub.6
H.sub.5 ##STR86## Cl (2-) Cl H ##STR87## Cl (2-) Cl CH.sub.3
##STR88## Cl (2-) Cl C.sub.2 H.sub.5 ##STR89## Cl (2-) Cl C.sub.3
H.sub.7 ##STR90## Cl (2-) Cl C.sub.3 H.sub.7 -i ##STR91## Cl (2-)
Cl C.sub.4 H.sub.9 ##STR92## Cl (2-) Cl C.sub.4 H.sub.9 -i
##STR93## Cl (2-) Cl C.sub.4 H.sub.9 -s ##STR94## Cl (2-) Cl
C.sub.4 H.sub.9 -t ##STR95## Cl (2-) Cl ##STR96## ##STR97## Cl (2-)
Cl ##STR98## ##STR99## Cl (2-) Cl CH.dbd.CHCH.sub.3 ##STR100## Cl
(2-) Cl ##STR101## ##STR102## Cl (2-) Cl ##STR103## ##STR104## Cl
(2-) Cl ##STR105## ##STR106## Cl (2-) Cl N(CH.sub.3).sub.2
##STR107## Cl (2-) Cl ##STR108## ##STR109## Cl (2-) Cl Cl
##STR110## Cl (2-) Cl Br ##STR111## SO.sub.2 CH.sub.3 (2-) Cl
CF.sub.3 ##STR112## SO.sub.2 CH.sub.3 (2-) Cl SCH.sub.3 ##STR113##
SO.sub.2 CH.sub.3 (2-) Cl SC.sub.2 H.sub.5 ##STR114## SO.sub.2
CH.sub.3 (2-) Cl SC.sub.3 H.sub.7 ##STR115## SO.sub.2 CH.sub.3 (2-)
Cl SC.sub.3 H.sub.7 -i ##STR116## SO.sub.2 CH.sub.3 (2-) Cl
##STR117## ##STR118## SO.sub.2 CH.sub.3 (2-) Cl ##STR119##
##STR120## SO.sub.2 CH.sub.3 (2-) Cl ##STR121## ##STR122## SO.sub.2
CH.sub.3 (2-) Cl ##STR123## ##STR124## SO.sub.2 CH.sub.3 (2-) Cl
##STR125## ##STR126## SO.sub.2 CH.sub.3 (2-) Cl
SCH.dbd.C.dbd.CH.sub.2 ##STR127## SO.sub.2 CH.sub.3 (2-) Cl
SCH.sub.2 CN ##STR128## SO.sub.2 CH.sub.3 (2-) Cl SCH.sub.2
CH.sub.2 CN ##STR129## SO.sub.2 CH.sub.3 (2-) Cl OCH.sub.3
##STR130## SO.sub.2 CH.sub.3 (2-) Cl OC.sub.2 H.sub.5 ##STR131##
SO.sub.2 CH.sub.3 (2-) Cl OC.sub.3 H.sub.7 ##STR132## SO.sub.2
CH.sub.3 (2-) Cl OC.sub.3 H.sub.7 -i ##STR133## SO.sub.2 CH.sub.3
(2-) Cl OC.sub.4 H.sub.9 ##STR134## SO.sub.2 CH.sub.3 (2-) Cl
OCH.sub.2 CF.sub.3 ##STR135## SO.sub.2 CH.sub.3 (2-) Cl ##STR136##
##STR137## SO.sub.2 CH.sub.3 (2-) Cl OC.sub.6 H.sub.5 ##STR138##
SO.sub.2 CH.sub.3 (2-) Cl H ##STR139## SO.sub.2 CH.sub.3 (2-) Cl
CH.sub.3 ##STR140## SO.sub.2 CH.sub.3 (2-) Cl C.sub.2 H.sub.5
##STR141## SO.sub.2 CH.sub.3 (2-) Cl C.sub.3 H.sub.7 ##STR142##
SO.sub.2 CH.sub.3 (2-) Cl C.sub.3 H.sub.7 -i ##STR143## SO.sub.2
CH.sub.3 (2-) Cl C.sub.4 H.sub.9 ##STR144## SO.sub.2 CH.sub.3 (2-)
Cl C.sub.4 H.sub.9 -i ##STR145## SO.sub.2 CH.sub.3 (2-) Cl C.sub.4
H.sub.9 -s ##STR146## SO.sub.2 CH.sub.3 (2-) Cl C.sub.4 H.sub.9 -t
##STR147## SO.sub.2 CH.sub.3 (2-) Cl ##STR148## ##STR149## SO.sub.2
CH.sub.3 (2-) Cl ##STR150## ##STR151## SO.sub.2 CH.sub.3 (2-) Cl
CH.dbd.CHCH.sub.3 ##STR152## SO.sub.2 CH.sub.3 (2-) Cl ##STR153##
##STR154## SO.sub.2 CH.sub.3 (2-) Cl ##STR155## ##STR156## SO.sub.2
CH.sub.3 (2-) Cl ##STR157## ##STR158## SO.sub.2 CH.sub.3 (2-) Cl
N(CH.sub.3).sub.2 ##STR159## SO.sub.2 CH.sub.3 (2-) Cl ##STR160##
##STR161## SO.sub.2 CH.sub.3 (2-) Cl Cl ##STR162## SO.sub.2
CH.sub.3 (2-) Cl Br ##STR163## Cl (2-) SO.sub.2 CH.sub.3 CF.sub.3
##STR164## Cl (2-) SO.sub.2 CH.sub.3 SCH.sub.3 ##STR165## Cl (2-)
SO.sub.2 CH.sub.3 SC.sub.2 H.sub.5 ##STR166## Cl (2-) SO.sub.2
CH.sub.3 SC.sub.3 H.sub.7 ##STR167## Cl (2-) SO.sub.2 CH.sub.3
SC.sub.3 H.sub.7 -i ##STR168## Cl (2-) SO.sub.2 CH.sub.3 ##STR169##
##STR170## Cl (2-) SO.sub.2 CH.sub.3 ##STR171## ##STR172## Cl (2-)
SO.sub.2 CH.sub.3 ##STR173## ##STR174## Cl (2-) SO.sub.2 CH.sub.3
##STR175## ##STR176## Cl (2-) SO.sub.2 CH.sub.3 ##STR177##
##STR178## Cl (2-) SO.sub.2 CH.sub.3 SCH.dbd.C.dbd.CH.sub.2
##STR179## Cl (2-) SO.sub.2 CH.sub.3 SCH.sub.2 CN ##STR180## Cl
(2-) SO.sub.2 CH.sub.3 SCH.sub.2 CH.sub.2 CN ##STR181## Cl (2-)
SO.sub.2 CH.sub.3 OCH.sub.3 ##STR182## Cl (2-) SO.sub.2 CH.sub.3
OC.sub.2 H.sub.5 ##STR183## Cl (2-) SO.sub.2 CH.sub.3 OC.sub.3
H.sub.7 ##STR184## Cl (2-) SO.sub.2 CH.sub.3 OC.sub.3 H.sub.7 -i
##STR185## Cl (2-) SO.sub.2 CH.sub.3 OC.sub.4 H.sub.9 ##STR186## Cl
(2-) SO.sub.2 CH.sub.3 OCH.sub.2 CF.sub.3 ##STR187## Cl (2-)
SO.sub.2 CH.sub.3 ##STR188## ##STR189## Cl (2-) SO.sub.2 CH.sub.3
OC.sub.6 H.sub.5 ##STR190## Cl (2-) SO.sub.2 CH.sub.3 H ##STR191##
Cl (2-) SO.sub.2 CH.sub.3 CH.sub.3 ##STR192## Cl (2-) SO.sub.2
CH.sub.3 C.sub.2 H.sub.5 ##STR193## Cl (2-) SO.sub.2 CH.sub.3
C.sub.3 H.sub.7 ##STR194## Cl (2-) SO.sub.2 CH.sub.3 C.sub.3
H.sub.7 -i ##STR195## Cl (2-) SO.sub.2 CH.sub.3 C.sub.4 H.sub.9
##STR196## Cl (2-) SO.sub.2 CH.sub.3 C.sub.4 H.sub.9 -i ##STR197##
Cl (2-) SO.sub.2 CH.sub.3 C.sub.4 H.sub.9 -s ##STR198## Cl (2-)
SO.sub.2 CH.sub.3 C.sub.4 H.sub.9 -t ##STR199## Cl (2-) SO.sub.2
CH.sub.3 ##STR200## ##STR201## Cl (2-) SO.sub.2 CH.sub.3 ##STR202##
##STR203## Cl (2-) SO.sub.2 CH.sub.3 CH.dbd.CHCH.sub.3 ##STR204##
Cl (2-) SO.sub.2 CH.sub.3 ##STR205## ##STR206## Cl (2-) SO.sub.2
CH.sub.3 ##STR207## ##STR208## Cl (2-) SO.sub.2 CH.sub.3 ##STR209##
##STR210## Cl (2-) SO.sub.2 CH.sub.3 N(CH.sub.3).sub.2 ##STR211##
Cl (2-) SO.sub.2 CH.sub.3 ##STR212## ##STR213## Cl (2-) SO.sub.2
CH.sub.3 Cl ##STR214## Cl (2-) SO.sub.2 CH.sub.3 Br ##STR215## Cl
(2-) Cl CF.sub.3 N(CH.sub.3).sub.2 Cl (2-) Cl SCH.sub.3
N(CH.sub.3).sub.2 Cl (2-) Cl SC.sub.2 H.sub.5 N(CH.sub.3).sub.2 Cl
(2-) Cl SC.sub.3 H.sub.7 N(CH.sub.3).sub.2 Cl (2-) Cl SC.sub.3
H.sub.7 -i N(CH.sub.3).sub.2 Cl (2-) Cl ##STR216##
N(CH.sub.3).sub.2 Cl (2-) Cl ##STR217## N(CH.sub.3).sub.2 Cl (2-)
Cl ##STR218## N(CH.sub.3).sub.2
Cl (2-) Cl ##STR219## N(CH.sub.3).sub.2 Cl (2-) Cl ##STR220##
N(CH.sub.3).sub.2 Cl (2-) Cl SCH.dbd.C.dbd.CH.sub.2
N(CH.sub.3).sub.2 Cl (2-) Cl SCH.sub.2 CN N(CH.sub.3).sub.2 Cl (2-)
Cl SCH.sub.2 CH.sub.2 CN N(CH.sub.3).sub.2 Cl (2-) Cl OCH.sub.3
N(CH.sub.3).sub.2 Cl (2-) Cl OC.sub.2 H.sub.5 N(CH.sub.3).sub.2 Cl
(2-) Cl OC.sub.3 H.sub.7 N(CH.sub.3).sub.2 Cl (2-) Cl OC.sub.3
H.sub.7 -i N(CH.sub.3).sub.2 Cl (2-) Cl OC.sub.4 H.sub.9
N(CH.sub.3).sub.2 Cl (2-) Cl OCH.sub.2 CF.sub.3 N(CH.sub.3).sub.2
Cl (2-) Cl ##STR221## N(CH.sub.3).sub.2 Cl (2-) Cl OC.sub.6 H.sub.5
N(CH.sub.3).sub.2 Cl (2-) Cl H N(CH.sub.3).sub.2 Cl (2-) Cl
CH.sub.3 N(CH.sub.3).sub.2 Cl (2-) Cl C.sub.2 H.sub.5
N(CH.sub.3).sub.2 Cl (2-) Cl C.sub.3 H.sub.7 N(CH.sub.3).sub.2 Cl
(2-) Cl C.sub.3 H.sub.7 -i N(CH.sub.3).sub.2 Cl (2-) Cl C.sub.4
H.sub.9 N(CH.sub.3).sub.2 Cl (2-) Cl C.sub.4 H.sub.9 -i
N(CH.sub.3).sub.2 Cl (2-) Cl C.sub.4 H.sub.9 -s N(CH.sub.3).sub.2
Cl (2-) Cl C.sub.4 H.sub.9 -t N(CH.sub.3).sub.2 Cl (2-) Cl
##STR222## N(CH.sub.3).sub.2 Cl (2-) Cl ##STR223##
N(CH.sub.3).sub.2 Cl (2-) Cl CH.dbd.CHCH.sub.3 N(CH.sub.3).sub.2 Cl
(2-) Cl ##STR224## N(CH.sub.3).sub.2 Cl (2-) Cl ##STR225##
N(CH.sub.3).sub.2 Cl (2-) Cl ##STR226## N(CH.sub.3).sub.2 Cl (2-)
Cl N(CH.sub.3).sub.2 N(CH.sub.3).sub.2 Cl (2-) Cl ##STR227##
N(CH.sub.3).sub.2 Cl (2-) Cl Cl N(CH.sub.3).sub.2 Cl (2-) Cl Br
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl CF.sub.3
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl SCH.sub.3
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl SC.sub.2 H.sub.5
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl SC.sub.3 H.sub.7
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl SC.sub.3 H.sub.7 -i
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl ##STR228##
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl ##STR229##
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl ##STR230##
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl ##STR231##
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl ##STR232##
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl SCH.dbd.C.dbd.CH.sub.2
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl SCH.sub.2 CN
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl SCH.sub.2 CH.sub.2 CN
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl OCH.sub.3
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl OC.sub.2 H.sub.5
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl OC.sub.3 H.sub.7
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl OC.sub.3 H.sub.7 -i
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl OC.sub.4 H.sub.9
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl OCH.sub.2 CF.sub.3
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl ##STR233##
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl OC.sub.6 H.sub.5
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl H N(CH.sub.3).sub.2
SO.sub.2 CH.sub.3 (2-) Cl CH.sub.3 N(CH.sub.3).sub.2 SO.sub.2
CH.sub.3 (2-) Cl C.sub.2 H.sub.5 N(CH.sub.3).sub.2 SO.sub.2
CH.sub.3 (2-) Cl C.sub.3 H.sub.7 N(CH.sub.3).sub.2 SO.sub.2
CH.sub.3 (2-) Cl C.sub.3 H.sub.7 -i N(CH.sub.3).sub.2 SO.sub.2
CH.sub.3 (2-) Cl C.sub.4 H.sub.9 N(CH.sub.3).sub.2 SO.sub.2
CH.sub.3 (2-) Cl C.sub.4 H.sub.9 -i N(CH.sub.3).sub.2 SO.sub.2
CH.sub.3 (2-) Cl C.sub.4 H.sub.9 -s N(CH.sub.3).sub.2 SO.sub.2
CH.sub.3 (2-) Cl C.sub.4 H.sub.9 -t N(CH.sub.3).sub.2 SO.sub.2
CH.sub.3 (2-) Cl ##STR234## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3
(2-) Cl ##STR235## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl
CH.dbd.CHCH.sub.3 N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl
##STR236## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl ##STR237##
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl ##STR238##
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl N(CH.sub.3).sub.2
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl ##STR239##
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) Cl Cl N(CH.sub.3).sub.2
SO.sub.2 CH.sub.3 (2-) Cl Br N(CH.sub.3).sub.2 Cl (2-) SO.sub.2
CH.sub.3 CF.sub.3 N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3
SCH.sub.3 N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 SC.sub.2
H.sub.5 N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 SC.sub.3
H.sub.7 N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 SC.sub.3
H.sub.7 -i N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 ##STR240##
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 ##STR241##
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 ##STR242##
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 ##STR243##
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 ##STR244##
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 SCH.dbd.C.dbd.CH.sub.2
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 SCH.sub.2 CN
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 SCH.sub.2 CH.sub.2 CN
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 OCH.sub.3
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 OC.sub.2 H.sub.5
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 OC.sub.3 H.sub.7
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 OC.sub.3 H.sub.7 -i
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 OC.sub.4 H.sub.9
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 OCH.sub.2 CF.sub.3
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 ##STR245##
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 OC.sub.6 H.sub.5
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 H N(CH.sub.3).sub.2 Cl
(2-) SO.sub.2 CH.sub.3 CH.sub.3 N(CH.sub.3).sub.2 Cl (2-) SO.sub.2
CH.sub.3 C.sub.2 H.sub.5 N(CH.sub.3).sub.2 Cl (2-) SO.sub.2
CH.sub.3 C.sub.3 H.sub.7 N(CH.sub.3).sub.2 Cl (2-) SO.sub.2
CH.sub.3 C.sub.3 H.sub.7 -i N(CH.sub.3).sub.2 Cl (2-) SO.sub.2
CH.sub.3 C.sub.4 H.sub.9 N(CH.sub.3).sub.2 Cl (2-) SO.sub.2
CH.sub.3 C.sub.4 H.sub.9 -i N(CH.sub.3).sub.2 Cl (2-) SO.sub.2
CH.sub.3 C.sub.4 H.sub.9 -s N(CH.sub.3).sub.2 Cl (2-) SO.sub.2
CH.sub.3 C.sub.4 H.sub.9 -t N(CH.sub.3).sub.2 Cl (2-) SO.sub.2
CH.sub.3 ##STR246## N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3
##STR247## N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3
CH.dbd.CHCH.sub.3 N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3
##STR248## N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 ##STR249##
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 ##STR250##
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 N(CH.sub.3).sub.2
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 ##STR251##
N(CH.sub.3).sub.2 Cl (2-) SO.sub.2 CH.sub.3 Cl N(CH.sub.3).sub.2 Cl
(2-) SO.sub.2 CH.sub.3 Br N(CH.sub.3).sub.2 Cl (2-) Cl CH.sub.3
OCH.sub.3 Cl (2-) Cl C.sub.2 H.sub.5 OCH.sub.3 Cl (2-) Cl C.sub.3
H.sub.7 OCH.sub.3 Cl (2-) Cl SCH.sub.3 OCH.sub.3 Cl (2-) Cl
SC.sub.2 H.sub.5 OCH.sub.3 Cl (2-) Cl OCH.sub.3 OCH.sub.3 Cl (2-)
Cl OC.sub.2 H.sub.5 OCH.sub.3 Cl (2-) Cl CH.sub.3 OC.sub.2 H.sub.5
Cl (2-) Cl C.sub.2 H.sub.5 OC.sub.2 H.sub.5 Cl (2-) Cl C.sub.3
H.sub.7 OC.sub.2 H.sub.5 Cl (2-) Cl SCH.sub.3 OC.sub.2 H.sub.5 Cl
(2-) Cl SC.sub.2 H.sub.5 OC.sub.2 H.sub.5 Cl (2-) Cl OCH.sub.3
OC.sub.2 H.sub.5 Cl (2-) Cl OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 Cl
(2-) SO.sub.2 CH.sub.3 CH.sub.3 OCH.sub.3 Cl (2-) SO.sub.2 CH.sub.3
C.sub.2 H.sub.5 OCH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 C.sub.3 H.sub.7
OCH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 SCH.sub.3 OCH.sub.3 Cl (2-)
SO.sub.2 CH.sub.3 SC.sub.2 H.sub.5 OCH.sub.3 Cl (2-) SO.sub.2
CH.sub.3 OCH.sub.3 OCH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 OC.sub.2
H.sub.5 OCH.sub.3 Cl (2-) SO.sub.2 CH.sub.3 CH.sub.3 OC.sub.2
H.sub.5 Cl (2-) SO.sub.2 CH.sub.3 C.sub.2 H.sub.5 OC.sub.2 H.sub.5
Cl (2-) SO.sub.2 CH.sub.3 C.sub.3 H.sub.7 OC.sub.2 H.sub.5 Cl (2-)
SO.sub.2 CH.sub.3 SCH.sub.3 OC.sub.2 H.sub.5 Cl (2-) SO.sub.2
CH.sub.3 SC.sub.2 H.sub.5 OC.sub.2 H.sub.5 Cl (2-) SO.sub.2
CH.sub.3 OCH.sub.3 OC.sub.2 H.sub.5 Cl (2-) SO.sub.2 CH.sub.3
OC.sub.2 H.sub.5 OC.sub.2 H.sub.5 SO.sub.2 CH.sub.3 (2-) Cl Cl
OCH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl Br OCH.sub.3 SO.sub.2 CH.sub.3
(2-) Cl CH.sub.3 OCH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl C.sub.2
H.sub.5 OCH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl C.sub.3 H.sub.7
OCH.sub.3 SO.sub.2 CH.sub.3 (2-) Cl SCH.sub.3 OCH.sub.3 SO.sub.2
CH.sub.3 (2-) Cl SC.sub.2 H.sub.5 OCH.sub.3 SO.sub.2 CH.sub.3 (2-)
Cl OCH.sub.3 OC.sub.2 H.sub.5 SO.sub.2 CH.sub.3 (2-) Cl OC.sub.2
H.sub.5 OC.sub.2 H.sub.5 SO.sub.2 CH.sub.3 (2-) Cl CH.sub.3
OC.sub.2 H.sub.5 SO.sub.2 CH.sub.3 (2-) Cl C.sub.2 H.sub.5 OC.sub.2
H.sub.5 SO.sub.2 CH.sub.3 (2-) Cl C.sub.3 H.sub.7 OC.sub.2 H.sub.5
SO.sub.2 CH.sub.3 (2-) Cl SCH.sub.3 OC.sub.2 H.sub.5 SO.sub.2
CH.sub.3 (2-) Cl SC.sub.2 H.sub.5 OC.sub.2 H.sub.5 SO.sub.2
CH.sub.3 (2-) Cl OCH.sub.3 OC.sub.2 H.sub.5 CF.sub.3 (2-) Cl Br
CH.sub.3 CF.sub.3 (2-) Cl SCH.sub.3 CH.sub.3 CF.sub.3 (2-) Cl
OCH.sub.3 CH.sub.3 CF.sub.3 (2-) Cl N(CH.sub.3).sub.2 CH.sub.3
CF.sub.3 (2-) Cl CF.sub.3 CH.sub.3 CF.sub.3 (2-) NO.sub.2 Br
CH.sub.3 CF.sub.3 (2-) NO.sub.2 SCH.sub.3 CH.sub.3 CF.sub.3 (2-)
NO.sub.2 OCH.sub.3 CH.sub.3 CF.sub.3 (2-) NO.sub.2
N(CH.sub.3).sub.2 CH.sub.3 CF.sub.3 (2-) NO.sub.2 CF.sub.3 CH.sub.3
CF.sub.3 (2-) CH.sub.3 Br CH.sub.3 CF.sub.3 (2-) CH.sub.3 SCH.sub.3
CH.sub.3 CF.sub.3 (2-) CH.sub.3 OCH.sub.3 CH.sub.3 CF.sub.3 (2-)
CH.sub.3 N(CH.sub.3).sub.2 CH.sub.3 CF.sub.3 (2-) CH.sub.3 CF.sub.3
CH.sub.3 CF.sub.3 (2-) OCH.sub.3 Br CH.sub.3 CF.sub.3 (2-)
OCH.sub.3 SCH.sub.3 CH.sub.3 CF.sub.3 (2-) OCH.sub.3 OCH.sub.3
CH.sub.3 CF.sub.3 (2-) OCH.sub.3 N(CH.sub.3).sub.2 CH.sub.3
CF.sub.3 (2-) OCH.sub.3 CF.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-)
NO.sub.2 Br CH.sub.3 SO.sub.2 CH.sub.3 (2-) NO.sub.2 SCH.sub.3
CH.sub.3 SO.sub.2 CH.sub.3 (2-) NO.sub.2 OCH.sub.3 CH.sub.3
SO.sub.2 CH.sub.3 (2-) NO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 SO.sub.2
CH.sub.3 (2-) NO.sub.2 CF.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-)
CF.sub.3 Br CH.sub.3 SO.sub.2 CH.sub.3 (2-) CF.sub.3 SCH.sub.3
CH.sub.3 SO.sub.2 CH.sub.3 (2-) CF.sub.3 OCH.sub.3 CH.sub.3
SO.sub.2 CH.sub.3 (2-) CF.sub.3 N(CH.sub.3).sub.2 CH.sub.3 SO.sub.2
CH.sub.3 (2-) CF.sub.3 CF.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-)
SO.sub.2 CH.sub.3 Br CH.sub.3 SO.sub.2 CH.sub.3 (2-) SO.sub.2
CH.sub.3 SCH.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-) SO.sub.2
CH.sub.3 OCH.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-) SO.sub.2
CH.sub.3 N(CH.sub.3).sub.2 CH.sub.3 SO.sub.2 CH.sub.3 (2-) SO.sub.2
CH.sub.3 CF.sub.3 CH.sub.3 CN (2-) Cl Br CH.sub.3 CN (2-) Cl
SCH.sub.3 CH.sub.3 CN (2-) Cl OCH.sub.3 CH.sub.3 CN (2-) Cl
N(CH.sub.3).sub.2 CH.sub.3 CN (2-) Cl CF.sub.3 CH.sub.3 CN (2-)
NO.sub.2 Br CH.sub.3 CN (2-) NO.sub.2 SCH.sub.3 CH.sub.3 CN (2-)
NO.sub.2 OCH.sub.3 CH.sub.3 CN (2-) NO.sub.2 N(CH.sub.3).sub.2
CH.sub.3 CN (2-) NO.sub.2 CF.sub.3 CH.sub.3 CN (2-) CF.sub.3 Br
CH.sub.3 CN (2-) CF.sub.3 SCH.sub.3 CH.sub.3 CN (2-) CF.sub.3
OCH.sub.3 CH.sub.3 CN (2-) CF.sub.3 N(CH.sub.3).sub.2 CH.sub.3 CN
(2-) CF.sub.3 CF.sub.3 CH.sub.3 CN (2-) SO.sub.2 CH.sub.3 Br
CH.sub.3 CN (2-) SO.sub.2 CH.sub.3 SCH.sub.3 CH.sub.3 CN (2-)
SO.sub.2 CH.sub.3 OCH.sub.3 CH.sub.3 CN (2-) SO.sub.2 CH.sub.3
N(CH.sub.3).sub.2 CH.sub.3
CN (2-) SO.sub.2 CH.sub.3 CF.sub.3 CH.sub.3 Br (2-) NO.sub.2 Br
CH.sub.3 Br (2-) NO.sub.2 SCH.sub.3 CH.sub.3 Br (2-) NO.sub.2
OCH.sub.3 CH.sub.3 Br (2-) NO.sub.2 N(CH.sub.3).sub.2 CH.sub.3 Br
(2-) NO.sub.2 CF.sub.3 CH.sub.3 Br (2-) CF.sub.3 Br CH.sub.3 Br
(2-) CF.sub.3 SCH.sub.3 CH.sub.3 Br (2-) CF.sub.3 OCH.sub.3
CH.sub.3 Br (2-) CF.sub.3 N(CH.sub.3).sub.2 CH.sub.3 Br (2-)
CF.sub.3 CF.sub.3 CH.sub.3 Br (2-) SO.sub.2 CH.sub.3 Br CH.sub.3 Br
(2-) SO.sub.2 CH.sub.3 SCH.sub.3 CH.sub.3 Br (2-) SO.sub.2 CH.sub.3
OCH.sub.3 CH.sub.3 Br (2-) SO.sub.2 CH.sub.3 N(CH.sub.3).sub.2
CH.sub.3 Br (2-) SO.sub.2 CH.sub.3 CF.sub.3 CH.sub.3 Br (2-)
CH.sub.3 Br CH.sub.3 Br (2-) CH.sub.3 SCH.sub.3 CH.sub.3 Br (2-)
CH.sub.3 OCH.sub.3 CH.sub.3 Br (2-) CH.sub.3 N(CH.sub.3).sub.2
CH.sub.3 Br (2-) CH.sub.3 CF.sub.3 CH.sub.3 Cl (2-) OCH.sub.3
CF.sub.3 CH.sub.3 Cl (2-) OCH.sub.3 SCH.sub.3 CH.sub.3 Cl (2-)
OCH.sub.3 SC.sub.2 H.sub.5 CH.sub.3 Cl (2-) OCH.sub.3 SC.sub.3
H.sub.7 CH.sub.3 Cl (2-) OCH.sub.3 SC.sub.3 H.sub.7 -i CH.sub.3 Cl
(2-) OCH.sub.3 ##STR252## CH.sub.3 Cl (2-) OCH.sub.3 ##STR253##
CH.sub.3 Cl (2-) OCH.sub.3 ##STR254## CH.sub.3 Cl (2-) OCH.sub.3
##STR255## CH.sub.3 Cl (2-) OCH.sub.3 ##STR256## CH.sub.3 Cl (2-)
OCH.sub.3 SCH.dbd.C.dbd.CH.sub.2 CH.sub.3 Cl (2-) OCH.sub.3
SCH.sub.2 CN CH.sub.3 Cl (2-) OCH.sub.3 SCH.sub.2 CH.sub.2 CN
CH.sub.3 Cl (2-) OCH.sub.3 OCH.sub.3 CH.sub.3 Cl (2-) OCH.sub.3
OC.sub.2 H.sub.5 CH.sub.3 Cl (2-) OCH.sub.3 OC.sub.3 H.sub.7
CH.sub.3 Cl (2-) OCH.sub.3 OC.sub.3 H.sub.7 -i CH.sub.3 Cl (2-)
OCH.sub.3 OC.sub.4 H.sub.9 CH.sub.3 Cl (2-) OCH.sub.3 OCH.sub.2
CF.sub.3 CH.sub.3 Cl (2-) OCH.sub.3 ##STR257## CH.sub.3 Cl (2-)
OCH.sub.3 OC.sub.6 H.sub.5 CH.sub.3 Cl (2-) OCH.sub.3 H CH.sub.3 Cl
(2-) OCH.sub.3 CH.sub.3 CH.sub.3 Cl (2-) OCH.sub.3 C.sub.2 H.sub.5
CH.sub.3 Cl (2-) OCH.sub.3 C.sub.3 H.sub.7 CH.sub.3 Cl (2-)
OCH.sub.3 C.sub.3 H.sub.7 -i CH.sub.3 Cl (2-) OCH.sub.3 C.sub.4
H.sub.9 CH.sub.3 Cl (2-) OCH.sub.3 C.sub.4 H.sub.9 -i CH.sub.3 Cl
(2-) OCH.sub.3 C.sub.4 H.sub.9 -s CH.sub.3 Cl (2-) OCH.sub.3
C.sub.4 H.sub.9 -t CH.sub.3 Cl (2-) OCH.sub.3 ##STR258## CH.sub.3
Cl (2-) OCH.sub.3 ##STR259## CH.sub.3 Cl (2-) OCH.sub.3
CH.dbd.CHCH.sub.3 CH.sub.3 Cl (2-) OCH.sub.3 ##STR260## CH.sub.3 Cl
(2-) OCH.sub.3 ##STR261## CH.sub.3 Cl (2-) OCH.sub.3 ##STR262##
CH.sub.3 Cl (2-) OCH.sub.3 N(CH.sub.3).sub.2 CH.sub.3 Cl (2-)
OCH.sub.3 ##STR263## CH.sub.3 Cl (2-) OCH.sub.3 Cl CH.sub.3 Cl (2-)
OCH.sub.3 Br CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 CF.sub.3
CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 SCH.sub.3 CH.sub.3
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 SC.sub.2 H.sub.5 CH.sub.3 SO.sub.2
CH.sub.3 (2-) OCH.sub.3 SC.sub.3 H.sub.7 CH.sub.3 SO.sub.2 CH.sub.3
(2-) OCH.sub.3 SC.sub.3 H.sub.7 -i CH.sub.3 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR264## CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
##STR265## CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 ##STR266##
CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 ##STR267## CH.sub.3
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 ##STR268## CH.sub.3 SO.sub.2
CH.sub.3 (2-) OCH.sub.3 SCH.dbd.C.dbd.CH.sub.2 CH.sub.3 SO.sub.2
CH.sub.3 (2-) OCH.sub.3 SCH.sub.2 CN CH.sub.3 SO.sub.2 CH.sub.3
(2-) OCH.sub.3 SCH.sub.2 CH.sub.2 CN CH.sub.3 SO.sub.2 CH.sub.3
(2-) OCH.sub.3 OCH.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
OC.sub.2 H.sub.5 CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OC.sub.3
H.sub.7 CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OC.sub.3 H.sub.7
-i CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OC.sub.4 H.sub.9
CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OCH.sub.2 CF.sub.3
CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 ##STR269## CH.sub.3
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OC.sub.6 H.sub.5 CH.sub.3 SO.sub.2
CH.sub.3 (2-) OCH.sub.3 H CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
CH.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.2 H.sub.5
CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.3 H.sub.7 CH.sub.3
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.3 H.sub.7 -i CH.sub.3
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.4 H.sub.9 CH.sub.3 SO.sub.2
CH.sub.3 (2-) OCH.sub.3 C.sub.4 H.sub.9 -i CH.sub.3 SO.sub.2
CH.sub.3 (2-) OCH.sub.3 C.sub.4 H.sub.9 -s CH.sub.3 SO.sub.2
CH.sub.3 (2-) OCH.sub.3 C.sub.4 H.sub.9 -t CH.sub.3 SO.sub.2
CH.sub.3 (2-) OCH.sub.3 ##STR270## CH.sub.3 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR271## CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
CH.dbd.CHCH.sub.3 CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
##STR272## CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 ##STR273##
CH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 ##STR274## CH.sub.3
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 N(CH.sub.3).sub.2 CH.sub.3
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 ##STR275## CH.sub.3 SO.sub.2
CH.sub.3 (2-) OCH.sub.3 Cl CH.sub.3 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 Br CH.sub.3 Cl (2-) OCH.sub.3 CF.sub.3 ##STR276## Cl (2-)
OCH.sub.3 SCH.sub.3 ##STR277## Cl (2-) OCH.sub.3 SC.sub.2 H.sub.5
##STR278## Cl (2-) OCH.sub.3 SC.sub.3 H.sub.7 ##STR279## Cl (2-)
OCH.sub.3 SC.sub.3 H.sub.7 -i ##STR280## Cl (2-) OCH.sub.3
##STR281## ##STR282## Cl (2-) OCH.sub.3 ##STR283## ##STR284## Cl
(2-) OCH.sub.3 ##STR285## ##STR286## Cl (2-) OCH.sub.3 ##STR287##
##STR288## Cl (2-) OCH.sub.3 ##STR289## ##STR290## Cl (2-)
OCH.sub.3 SCH.dbd.C.dbd.CH.sub.2 ##STR291## Cl (2-) OCH.sub.3
SCH.sub.2 CN ##STR292## Cl (2-) OCH.sub.3 SCH.sub.2 CH.sub.2 CN
##STR293## Cl (2-) OCH.sub.3 OCH.sub.3 ##STR294## Cl (2-) OCH.sub.3
OC.sub.2 H.sub.5 ##STR295## Cl (2-) OCH.sub.3 OC.sub.3 H.sub.7
##STR296## Cl (2-) OCH.sub.3 OC.sub.3 H.sub.7 -i ##STR297## Cl (2-)
OCH.sub.3 OC.sub.4 H.sub.9 ##STR298## Cl (2-) OCH.sub.3 OCH.sub.2
CF.sub.3 ##STR299## Cl (2-) OCH.sub.3 ##STR300## ##STR301## Cl (2-)
OCH.sub.3 OC.sub.6 H.sub.5 ##STR302## Cl (2-) OCH.sub.3 H
##STR303## Cl (2-) OCH.sub.3 CH.sub.3 ##STR304## Cl (2-) OCH.sub.3
C.sub.2 H.sub.5 ##STR305## Cl (2-) OCH.sub.3 C.sub.3 H.sub.7
##STR306## Cl (2-) OCH.sub.3 C.sub.3 H.sub.7 -i ##STR307## Cl (2-)
OCH.sub.3 C.sub.4 H.sub.9 ##STR308## Cl (2-) OCH.sub.3 C.sub.4
H.sub.9 -i ##STR309## Cl (2-) OCH.sub.3 C.sub.4 H.sub.9 -s
##STR310## Cl (2-) OCH.sub.3 C.sub.4 H.sub.9 -t ##STR311## Cl (2-)
OCH.sub.3 ##STR312## ##STR313## Cl (2-) OCH.sub.3 ##STR314##
##STR315## Cl (2-) OCH.sub.3 CH.dbd.CHCH.sub.3 ##STR316## Cl (2-)
OCH.sub.3 ##STR317## ##STR318## Cl (2-) OCH.sub.3 ##STR319##
##STR320## Cl (2-) OCH.sub.3 ##STR321## ##STR322## Cl (2-)
OCH.sub.3 N(CH.sub.3).sub.2 ##STR323## Cl (2-) OCH.sub.3 ##STR324##
##STR325## Cl (2-) OCH.sub.3 Cl ##STR326## Cl (2-) OCH.sub.3 Br
##STR327## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 CF.sub.3 ##STR328##
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 SCH.sub.3 ##STR329## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 SC.sub.2 H.sub.5 ##STR330## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 SC.sub.3 H.sub.7 ##STR331## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 SC.sub.3 H.sub.7 -i ##STR332## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 ##STR333## ##STR334## SO.sub.2 CH.sub.3
(2-) OCH.sub.3 ##STR335## ##STR336## SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR337## ##STR338## SO.sub.2 CH.sub.3 (2-) OCH.sub.3
##STR339## ##STR340## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 ##STR341##
##STR342## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 SCH.dbd.C.dbd.CH.sub.2
##STR343## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 SCH.sub.2 CN ##STR344##
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 SCH.sub.2 CH.sub.2 CN ##STR345##
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OCH.sub.3 ##STR346## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 OC.sub.2 H.sub.5 ##STR347## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 OC.sub.3 H.sub.7 ##STR348## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 OC.sub.3 H.sub.7 -i ##STR349## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 OC.sub.4 H.sub.9 ##STR350## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 OCH.sub.2 CF.sub.3 ##STR351## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 ##STR352## ##STR353## SO.sub.2 CH.sub.3
(2-) OCH.sub.3 OC.sub.6 H.sub.5 ##STR354## SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 H ##STR355## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 CH.sub.3
##STR356## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.2 H.sub.5
##STR357## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.3 H.sub.7
##STR358## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.3 H.sub.7 -i
##STR359## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.4 H.sub.9
##STR360## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.4 H.sub.9 -i
##STR361## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.4 H.sub.9 -s
##STR362## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.4 H.sub.9 -t
##STR363## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 ##STR364## ##STR365##
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 ##STR366## ##STR367## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 CH.dbd.CHCH.sub.3 ##STR368## SO.sub.2
CH.sub.3 (2-) OCH.sub.3 ##STR369## ##STR370## SO.sub.2 CH.sub.3
(2-) OCH.sub.3 ##STR371## ##STR372## SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR373## ##STR374## SO.sub.2 CH.sub.3 (2-) OCH.sub.3
N(CH.sub.3).sub.2 ##STR375## SO.sub.2 CH.sub.3 (2-) OCH.sub.3
##STR376## ##STR377## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 Cl
##STR378## SO.sub.2 CH.sub.3 (2-) OCH.sub.3 Br ##STR379## Cl (2-)
OCH.sub.3 CF.sub.3 N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 SCH.sub.3
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 SC.sub.2 H.sub.5
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 SC.sub.3 H.sub.7
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 SC.sub.3 H.sub.7 -i
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 ##STR380## N(CH.sub.3).sub.2 Cl
(2-) OCH.sub.3 ##STR381## N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3
##STR382## N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 ##STR383##
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 ##STR384## N(CH.sub.3).sub.2 Cl
(2-) OCH.sub.3 SCH.dbd.C.dbd.CH.sub.2 N(CH.sub.3).sub.2 Cl (2-)
OCH.sub.3 SCH.sub.2 CN N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3
SCH.sub.2 CH.sub.2 CN N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 OCH.sub.3
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 OC.sub.2 H.sub.5
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 OC.sub.3 H.sub.7
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 OC.sub.3 H.sub.7 -i
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 OC.sub.4 H.sub.9
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 OCH.sub.2 CF.sub.3
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 ##STR385## N(CH.sub.3).sub.2 Cl
(2-) OCH.sub.3 OC.sub.6 H.sub.5 N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3
H N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 CH.sub.3 N(CH.sub.3).sub.2 Cl
(2-) OCH.sub.3 C.sub.2 H.sub.5 N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3
C.sub.3 H.sub.7 N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 C.sub.3 H.sub.7
-i N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 C.sub.4 H.sub.9
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 C.sub.4 H.sub.9 -i
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 C.sub.4 H.sub.9 -s
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 C.sub.4 H.sub.9 -t
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 ##STR386## N(CH.sub.3).sub.2 Cl
(2-) OCH.sub.3 ##STR387## N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3
CH.dbd.CHCH.sub.3 N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 ##STR388##
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 ##STR389## N(CH.sub.3).sub.2 Cl
(2-) OCH.sub.3 ##STR390## N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3
N(CH.sub.3).sub.2 N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 ##STR391##
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 Cl N(CH.sub.3).sub.2 Cl (2-)
OCH.sub.3 Br N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
CF.sub.3 N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
SCH.sub.3 N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
SC.sub.2 H.sub.5 N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
SC.sub.3 H.sub.7 N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
SC.sub.3 H.sub.7 -i N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR392## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR393## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR394## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR395## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR396## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 SCH.dbd.C.dbd.CH.sub.2 N(CH.sub.3).sub.2 SO.sub.2
CH.sub.3 (2-) OCH.sub.3 SCH.sub.2 CN N(CH.sub.3).sub.2 SO.sub.2
CH.sub.3 (2-) OCH.sub.3 SCH.sub.2 CH.sub.2 CN N(CH.sub.3).sub.2
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OCH.sub.3 N(CH.sub.3).sub.2
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OC.sub.2 H.sub.5 N(CH.sub.3).sub.2
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OC.sub.3 H.sub.7 N(CH.sub.3).sub.2
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OC.sub.3 H.sub.7 -i
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OC.sub.4 H.sub.9
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OCH.sub.2
CF.sub.3 N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
##STR397## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
OC.sub.6 H.sub.5 N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
H N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 CH.sub.3
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.2 H.sub.5
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.3 H.sub.7
N(CH.sub.3).sub.2
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.3 H.sub.7 -i
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.4 H.sub.9
N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.4 H.sub.9
-i N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.4
H.sub.9 -s N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
C.sub.4 H.sub.9 -t N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR398## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR399## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 CH.dbd.CHCH.sub.3 N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3
(2-) OCH.sub.3 ##STR400## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR401## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 ##STR402## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 N(CH.sub.3).sub.2 N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3
(2-) OCH.sub.3 ##STR403## N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-)
OCH.sub.3 Cl N(CH.sub.3).sub.2 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 Br
N(CH.sub.3).sub.2 Cl (2-) OCH.sub.3 CH.sub.3 OCH.sub.3 Cl (2-)
OCH.sub.3 C.sub.2 H.sub.5 OCH.sub.3 Cl (2-) OCH.sub.3 C.sub.3
H.sub.7 OCH.sub.3 Cl (2-) OCH.sub.3 SCH.sub.3 OCH.sub.3 Cl (2-)
OCH.sub.3 SC.sub.2 H.sub.5 OCH.sub.3 Cl (2-) OCH.sub.3 OCH.sub.3
OCH.sub.3 Cl (2-) OCH.sub.3 OC.sub.2 H.sub.5 OCH.sub.3 Cl (2-)
OCH.sub.3 CH.sub.3 OC.sub.2 H.sub.5 Cl (2-) OCH.sub.3 C.sub.2
H.sub.5 OC.sub.2 H.sub.5 Cl (2-) OCH.sub.3 C.sub.3 H.sub.7 OC.sub.2
H.sub.5 Cl (2-) OCH.sub.3 SCH.sub.3 OC.sub.2 H.sub.5 Cl (2-)
OCH.sub.3 SC.sub.2 H.sub.5 OC.sub.2 H.sub.5 Cl (2-) OCH.sub.3
OCH.sub.3 OC.sub.2 H.sub.5 Cl (2-) OCH.sub.3 OC.sub.2 H.sub.5
OC.sub.2 H.sub.5 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 Cl OCH.sub.3
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 Br OCH.sub.3 SO.sub.2 CH.sub.3
(2-) OCH.sub.3 CH.sub.3 OCH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3
C.sub.2 H.sub.5 OCH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.3
H.sub.7 OCH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 SCH.sub.3
OCH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 SC.sub.2 H.sub.5
OCH.sub.3 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OCH.sub.3 OC.sub.2
H.sub.5 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OC.sub.2 H.sub.5 OC.sub.2
H.sub.5 SO.sub.2 CH.sub.3 (2-) OCH.sub.3 CH.sub.3 OC.sub.2 H.sub.5
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.2 H.sub.5 OC.sub.2 H.sub.5
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 C.sub.3 H.sub.7 OC.sub.2 H.sub.5
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 SCH.sub.3 OC.sub.2 H.sub.5
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 SC.sub.2 H.sub.5 OC.sub.2 H.sub.5
SO.sub.2 CH.sub.3 (2-) OCH.sub.3 OCH.sub.3 OC.sub.2 H.sub.5
Group 3
##STR404##
R.sup.3, (R.sup.4).sub.n, R.sup.5 and R.sup.6 have, for example,
the meanings given above in Group 1.
Group 4
##STR405##
R.sup.3, (R.sup.4).sub.n, R.sup.5 and R.sup.6 have, for example,
the meanings given above in Group 2.
The novel substituted benzoyl ketones of the general formula (I)
have strong and selective herbicidal activity.
The novel substituted benzoyl ketones of the general formula (I)
are obtained when: (a) ketones of the general formula (II)
##STR406## in which R.sup.1 and R.sup.2 are each as defined above,
are reacted with substituted benzoic acids of the general formula
(III) ##STR407## in which n, A, R.sup.3, R.sup.4 and Z are each as
defined above, if appropriate in the presence of one or more
reaction auxiliaries and if appropriate in the presence of one or
more diluents, or when (b) benzoylisoxazoles of the general formula
(IV) ##STR408## in which n, A, R.sup.1, R.sup.2, R.sup.3, R.sup.4
and Z are each as defined above, are isomerized in the presence of
one or more reaction auxiliaries and if appropriate in the presence
of one or more diluents, and electrophilic or nucleophilic
substitutions and/or oxidations or reductions within the scope of
the definition of the substituents are, if appropriate,
subsequently, i.e. after the processes (a) or (b) according to the
invention have been carried out, carried out in a customary manner
on the resulting compounds of the formula (I), or the compounds of
the formula (I) are converted in a customary manner into salts.
The compounds of the formula (I) can be converted by customary
methods into other compounds of the formula (I) according to the
definition above, for example by nucleophilic substitution (for
example R.sup.5 : Cl.fwdarw.OC.sub.2 H.sub.5, SCH.sub.3) or by
oxidation (for example R.sup.5 : CH.sub.2 SCH.sub.3.fwdarw.CH.sub.2
S(O)CH.sub.3).
In principle, the compounds of the general formula (I) can also be
synthesized as outlined below:
Reaction of ketones of the general formula (II)--above--with
reactive derivatives of the substituted benzoic acids of the
general formula (I)--above--, in particular with appropriate
carbonyl chlorides, carboxylic anhydrides, carboxylic acid
cyanides, methyl carboxylates or ethyl carboxylates--if appropriate
in the presence of reaction auxiliaries, such as, for example,
triethylamine (and, if appropriate, additionally zinc chloride),
and if appropriate in the presence of a diluent, such as, for
example, methylene chloride: ##STR409##
Using, for example, ethyl methylsulfonylmethyl ketone and
2-(3-carboxy-5-fluorobenzyl)-5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazo
l-3-one as starting materials, the course of the reaction in the
process (a) according to the invention can be illustrated by the
following formula scheme: ##STR410##
Using, for example,
(5-cyclopropyl-isoxazol-4-yl)-[2-(4-methyl-3-methylthio-5-oxo-4,5-dihydro-
[1,2,4]-triazol-1-yl-methyl)-4-trifluoromethyl-phenyl]-methanone as
starting material, the course of the reaction in the process (b)
according to the invention can be illustrated by the following
formula scheme: ##STR411##
The formula (II) provides a general definition of the ketones to be
used as starting materials in the process (a) according to the
invention for preparing compounds of the general formula (I). In
the general formula (II), R.sup.1 and R.sup.2 each preferably have
those meanings which have already been mentioned above, in
connection with the description of the compounds of the general
formula (I) according to the invention, as being preferred,
particularly preferred, very particularly preferred or most
preferred for R.sup.1 and R.sup.2.
The starting materials of the general formula (II) are known and/or
can be prepared by processes known per se (cf. the Preparation
Examples).
The formula (III) provides a general definition of the substituted
benzoic acids further to be used as starting materials in the
process (a) according to the invention for preparing compounds of
the formula (I). In the formula (III), n, A, R.sup.3, R.sup.4 and Z
each preferably have those meanings which have already been
mentioned above, in connection with the description of the
compounds of the formula (I) according to the invention, as being
preferred, particularly preferred, very particularly preferred or
most preferred for n, A, R.sup.3, R.sup.4 and Z.
The starting materials of the general formula (m), except for
2-(5-carboxy-2,4-dichloro-phenyl)-4-difluoromethyl-5-methyl-2,4-dihydro-3H
-1,2,4-triazol-3-one--alias
2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triaz
ol-1-yl)-benzoic acid (CAS-Reg.-No. 90208-77-8)--and
2-(5-carboxy-2,4-dichlorophenyl)4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazol-
3-one --alias
2,4-dichloro-5-(4,5-dihydro-3,4-dimethyl-5-oxo-1H-1,2,4-triazol-1-yl)-benz
oic acid (CAS-Reg.-No. 90208-76-7)--have hitherto not been
disclosed in the literature. Except for
2-(5-carboxy-2,4-dichloro-phenyl)-4-difluoromethyl-5-methyl-2,4-dihydro-3H
-1,2,4-triazol-3-one and
2-(5-carboxy-2,4-dichloro-phenyl)-4,5-dimethyl-2,4-dihydro-3H-1,2,4-triazo
l-3-one (cf. JP-A-58225070--cited in Chem. Abstracts 100:209881,
JP-A-02015069--cited in Chem. Abstracts 113:23929) they are,
however, part of the subject-matter of an earlier but not
prior-published application (cf. DE-A-19833360).
The substituted benzoic acids of the general formula (E) are
obtained when benzoic acid derivatives of the general formula (V)
##STR412##
in which n, A, R.sup.3 and R.sup.4 and Z are each as defined above
and X.sup.1 represents cyano, carbamoyl or alkoxycarbonyl, are
reacted with water, if appropriate in the presence of a hydrolysis
auxiliary, such as, for example, sulfuric acid, at temperatures
between 50.degree. C. and 120.degree. C. (cf. the Preparation
Examples).
The benzoic acid derivatives of the general formula (V) required as
precursors are known and/or can be prepared by processes known per
se (cf. DE-A-3839480, DE-A-4239296, EP-A-597360, EP-A-609734,
DE-A-4303676, EP-A-617026, DE-A-4405614, U.S. Pat. No.
5,378,681).
The novel substituted benzoic acids of the general formula (III)
are also obtained when halogeno(alkyl)benzoic acids of the general
formula (VI) ##STR413##
in which n, A, R.sup.3 and R.sup.4 are each as defined above and X
represents halogen (in particular chlorine or bromine) are reacted
with compounds of the general formula (VII), ##STR414##
in which Z is as defined above, if appropriate in the presence of a
reaction auxiliary, such as, for example, triethylamine or
potassium carbonate, and if appropriate in the presence of a
diluent, such as, for example, acetone, acetonitrile,
N,N-dimethyl-formamide or N,N-dimethyl-acetamide, at temperatures
between 50.degree. C. and 200.degree. C. (cf. the Preparation
Examples).
In place of the halogeno(alkyl)benzoic acids of the general formula
(VI) it is also possible to react the corresponding nitrites,
amides and esters--in particular the methyl esters or the ethyl
esters--analogously to the method described above with compounds of
the general formula (VII). By subsequent hydrolysis according to
customary methods, for example by reaction with aqueous/ethanol
potassium hydroxide solution, it is then possible to obtain the
corresponding substituted benzoic acids.
The halogeno(alkyl)benzoic acids of the formula (VI)--or the
corresponding nitriles or esters--required as precursors are known
and/or can be prepared by processes known per se (cf. EP-A-90369,
EP-A-93488, EP-A-399732, EP-A-480641, EP-A-609798, EP-A-763524,
DE-A-2126720, WO-A-93/03722, WO-A-97/38977, U.S. Pat. No.
3,978,127, U.S. Pat. No. 4,837,333).
The compounds of the general formula (VII) further required as
precursors are known and/or can be prepared by processes known per
se.
The process (a) according to the invention for preparing the novel
substituted benzoyl ketones of the general formula (I) is, if
appropriate, carried out using one or more reaction
auxiliaries.
Examples of these which may be mentioned are sodium cyanide,
potassium cyanide, acetone cyanohydrin, imidazole, triazole,
diethyl cyanophosphonate, 2-cyano-2-(trimethylsilyloxy)-propane and
trimethylsilyl cyanide.
Particularly suitable reaction auxiliaries which may be mentioned
are diethyl cyanophosphonate and trimethylsilyl cyanide.
The processes (a) and (b) according to the invention for preparing
the novel substituted benzoyl ketones of the general formula (I)
are, if appropriate, carried out using a (further) reaction
auxiliary. Suitable (further) reaction auxiliaries for the
processes according to the invention are, in general, basic organic
nitrogen compounds, such as, for example, trimethylamine,
triethylamine, tripropylamine, tributylamine,
ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine,
dicyclohexylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline,
N,N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-,
4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3,4-dimethyl- and
3,5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine,
4-dimethylamino-pyridine, N-methyl-piperidine,
1,4-diazabicyclo[2.2.2]-octane (DABCO),
1,5-diazabicyclo[4.3.0]-non-5-ene (DBN) or
1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU).
Suitable diluents for carrying out the processes (a) and (b)
according to the invention are especially inert organic solvents.
These include, in particular, aliphatic, alicyclic or aromatic,
optionally halogenated hydrocarbons, such as, for example, benzine,
benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum
ether, hexane, cyclohexane, dichloromethane, chloroform, carbon
tetrachloride or 1,2-dichloroethane; ethers, such as diethyl ether,
diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol
dimethyl ether or ethylene glycol diethyl ether; ketones, such as
acetone, butanone or methyl isobutyl ketone; nitriles, such as
acetonitrile, propionitrile or butyronitrile; amides, such as
N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide,
N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters, such
as methyl acetate or ethyl acetate; sulphoxides, such as dimethyl
sulphoxide.
When carrying out the processes (a) and (b) according to the
invention, the reaction temperatures can be varied within a
relatively wide range. In general, the reactions are carried out at
temperatures between 0.degree. C. and 150.degree. C., preferably
between 10.degree. C. and 120.degree. C.
The processes (a) and (b) according to the invention are generally
carried out under atmospheric pressure. However, it is also
possible to carry out the processes according to the invention
under elevated or reduced pressure--in general between 0.1 bar and
10 bar.
For carrying out the processes (a) and (b) according to the
invention, the starting materials are generally employed in
approximately equimolar amounts. However, it is also possible to
employ a relatively large excess of one of the components. The
reaction is generally carried out in a suitable diluent in the
presence of a dehydrating agent, and the reaction mixture is
generally stirred at the required temperature for several hours.
Work-up is carried out by customary methods (cf. the Preparation
Examples).
The active compounds according to the invention can be used as
defoliants, desiccants, haulm killers and, especially, as weed
killers. By weeds in the broadest sense there are to be understood
all plants which grow in locations where they are undesired.
Whether the substances according to the invention act as total or
selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for
example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium,
Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica,
Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea,
Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum,
Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex,
Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium,
Ranunculus, Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta,
Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia,
Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis,
Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria,
Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria,
Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon,
Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus,
Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis,
Alopecurus, Apera, Aegilops, Phalaris.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum,
Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas,
Asparagus, Allium.
However, the use of the active compounds according to the invention
is in no way restricted to these genera, but also extends in the
same manner to other plants.
Depending on the concentration, the active compounds according to
the invention are suitable for total weed control, for example on
industrial terrain and rail tracks and on paths and areas with or
without tree growth. Equally, the active compounds according to the
invention can be employed for controlling weeds in perennial crops,
for example forests, ornamental tree plantings, orchards,
vineyards, citrus groves, nut orchards, banana plantations, coffee
plantations, tea plantations, rubber plantations, oil palm
plantations, cocoa plantations, soft fruit plantings and hop
fields, on lawns and turf and pastures and for selective weed
control in annual crops.
The compounds of the formula (I) according to the invention have
strong herbicidal activity and a broad activity spectrum when used
on the soil and on above-ground parts of plants. To a certain
extent, they are also suitable for selective control of
monocotyledonous and dicotyledonous weeds in monocotyledonous and
dicotyledonous crops, both by the pre-emergence and by the
post-emergence method.
The active compounds can be converted into the customary
formulations, such as solutions, emulsions, wettable powders,
suspensions, powders, dusts, pastes, soluble powders, granules,
suspo-emulsion concentrates, natural and synthetic substances
impregnated with active compound, and microencapsulations in
polymeric substances.
These formulations are produced in a known manner, for example by
mixing the active compounds with extenders, that is to say liquid
solvents and/or solid carriers, optionally with the use of
surfactants, that is to say emulsifiers and/or dispersants and/or
foam formers.
If the extender used is water, it is also possible to use, for
example, organic solvents as auxiliary solvents. Liquid solvents
which are mainly suitable are: aromatics, such as xylene, toluene
or alkylnaphthalenes, chlorinated aromatics and chlorinated
aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or
methylene chloride, aliphatic hydrocarbons, such as cyclohexane or
paraffins, for example petroleum fractions, mineral and vegetable
oils, alcohols, such as butanol or glycol, and also their ethers
and esters, ketones, such as acetone, methyl ethyl ketone, methyl
isobutyl ketone or cyclohexanone, strongly polar solvents, such as
dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground
natural minerals, such as kaolins, clays, talc, chalk, quartz,
attapulgite, montmorillonite or diatomaceous earth, and ground
synthetic minerals, such as finely divided silica, alumina and
silicates; suitable solid carriers for granules are: for example
crushed and fractionated natural rocks, such as calcite, marble,
pumice, sepiolite, dolomite and synthetic granules of inorganic and
organic meals, and granules of organic material, such as sawdust,
coconut shells, maize cobs and tobacco stalks; suitable emulsifiers
and/or foam formers are: for example nonionic and anionic
emulsifiers, such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol ethers, for example alkylaryl
polyglycol ethers, alkylsulphonates, alkyl sulphates,
arylsulphonates and protein hydrolysates; suitable dispersants are:
for example lignosulphite waste liquors and methylcellulose.
Tackifiers, such as carboxymethylcellulose, natural and synthetic
polymers in the form of powders, granules or latices, such as gum
arabic, polyvinyl alcohol and polyvinyl acetate, and also natural
phospholipids, such as cephalins and lecithins, and synthetic
phospholipids can be used in the formulations. Other possible
additives are mineral and vegetable oils.
It is possible to use dyestuffs, such as inorganic pigments, for
example iron oxide, titanium oxide, Prussian blue, and organic
dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal
phthalocyanine dyestuffs, and trace nutrients, such as salts of
iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by
weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the
invention, as such or in the form of their formulations, can also
be used as mixtures with known herbicides, finished formulations or
tank mixes being possible.
Possible components for the mixtures are known herbicides, for
example acetochlor, acifluorfen(-sodium), aclonifen, alachlor,
alloxydim(-sodium), ametryne, amicarbazone, amidochlor,
amidosulfuron, anilofos, asulam, atrazine, azafenidin,
azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl),
bentazon, benzobicyclon, benzofenap, benzoylprop(-ethyl),
bialaphos, bifenox, bispyribac(-sodium), bromobutide, bromofenoxim,
bromoxynil, butachlor, butroxydim, butylate, cafenstrole,
caloxydim, carbetamide, carfentrazone(-ethyl), chlomethoxyfen,
chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen,
chlorsulfuron, chlortoluron, cinidon(-ethyl), cinmethylin,
cinosulfuron, clethodim, clodinafop(-propargyl), clomazone,
clomeprop, clopyralid, clopyrasulfuron(-methyl),
cloransulam(-methyl), cumyluron, cyanazine, cybutryne, cycloate,
cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB,
2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl),
diclosulam, diethatyl(-ethyl), difenzoquat, diflufenican,
diflufenzopyr, dimefuron, dimepiperate, dimethachlor,
dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid,
diquat, dithiopyr, diuron, dymron, epoprodan, EPTC, esprocarb,
ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen,
ethoxysulfuron, etobenzanid, fenoxaprop(-P-ethyl),
flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl),
flazasulfuron, fluazifop(-P-butyl), fluazolate, flucarbazone,
flufenacet, flumetsulam, flumiclorac(-pentyl), flumioxazin,
flumipropyn, flumetsulam, fluometuron, fluorochloridone,
fluoroglycofen(-ethyl), flupoxam, flupropacil,
flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone,
fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthiacet(-methyl),
fluthiamide, fomesafen, glufosinate(-ammonium),
glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl),
haloxyfop(-p-methyl), hexazinone, imazamethabenz(-methyl),
imazamethapyr, imazamox, imazapic, imazapyr, imazaquin,
imazethapyr, imazosulfuron, iodosulfuron, ioxynil, isopropalin,
isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole,
isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet,
mesotrione, metamitron, metazachlor, methabenzthiazuron,
metobenzuron, metobromuron, (alpha-)metolachlor, metosulam,
metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron,
naproanilide, napropamide, neburon, nicosulfuron, norflurazon,
orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron,
oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid,
pendimethalin, pentoxazone, phenmedipham, picolinafen, piperophos,
pretilachlor, primisulfuron(-methyl), prometryn, propachlor,
propanil, propaquizafop, propisochlor, propyzamide, prosulfocarb,
prosulfuron, pyraflufen(-ethyl), pyrazolate,
pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb,
pyridate, pyriminobac(-methyl), pyrithiobac(-sodium), quinchlorac,
quinmerac, quinoclamine, quizalofop(-P-ethyl),
quizalofop(-P-tefuryl), rimsulfuron, sethoxydim, simazine,
simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl),
sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim,
terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr,
thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil,
tralkoxydim, triallate, triasulfuron, tribenuron(-methyl),
triclopyr, tridiphane, trifluralin, triflusulfuron,
tritosulfuron.
A mixture with other known active compounds, such as fungicides,
insecticides, acaricides, nematicides, bird repellents, plant
nutrients and agents which improve soil structure, is also
possible.
The active compounds can be used as such, in the form of their
formulations or in the use forms prepared therefrom by further
dilution, such as ready-to-use solutions, suspensions, emulsions,
powders, pastes and granules. They are used in the customary
manner, for example by watering, spraying, atomizing,
scattering.
The active compounds according to the invention can be applied both
before and after emergence of the plants. They can also be
incorporated into the soil before sowing.
The amount of active compound used can vary within a relatively
wide range. It depends essentially on the nature of the desired
effect. In general, the amounts used are between 1 g and 10 kg of
active compound per hectare of soil surface, preferably between 5 g
and 5 kg per ha.
The preparation and the use of the active compounds according to
the invention can be seen from the examples below.
PREPARATION EXAMPLE
Example 1
##STR415##
2.38 g (6.4 mmol) of
4-cyclopropyl-5-ethoxy-2-(2-carboxy-5-trifluoromethyl-benzyl)-2,4-dihydro-
3H-1,2,4-triazol-3-one are initially charged in 20 ml of
N,N-dimethyl-formamide and, at room temperature (approximately
20.degree. C.), admixed successively with stirring with 0.7 g (6.4
mmol) of cyanomethyl cyclopropyl ketone, 2.7 ml (19 mmol) of
triethylamine and 1.04 g (6.4 mmol) of diethyl cyanophosphonate.
The reaction mixture is stirred at room temperature for two days,
poured into about twice the amount of water, acidified with 2 N
hydrochloric acid and shaken with methylene chloride. The organic
phase is separated off, washed with 2 N hydrochloric acid, dried
with sodium sulphate and filtered. The filtrate is concentrated and
the residue is purified by column chromatography (silica gel,
hexane/ethyl acetate, vol.: 4/1).
This gives 1.18 g (40% of theory) of
3-cyclopropyl-2-{2-[4-(cyclopropyl-3-ethoxy-5-oxo-4,5-dihydro-1H-1,2,4-tri
azol-1-yl)-methyl]4-trifluoromethyl-benzoyl}-3-oxo-propanenitrile
as an amorphous product.
logP (determined at pH=2): 3.35.
Analogously to Example 1, and in accordance with the general
description of the preparation process according to the invention,
it is also possible to prepare, for example, the compounds of the
general formula (I)--or of the formulae (IA-3), (IB-3),
(IC-3)--listed in Tables 1 and 1a below. ##STR416##
TABLE 1 Examples of the compounds of the formulae (IA-3), (IB-3)
and (IC-3) (formula) Ex. (position) Physical No. A Q R.sup.1
R.sup.2 R.sup.3 (R.sup.4).sub.n R.sup.5 R.sup.6 data 2 CH.sub.2 O
##STR417## CN CF.sub.3 -- SCH.sub.3 ##STR418## (IA) logP =
2.92.sup.a) 3 CH.sub.2 O ##STR419## CN CF.sub.3 -- OC.sub.2 H.sub.5
CH.sub.3 (IA) logP = 3.03.sup.a) 4 CH.sub.2 O ##STR420## CN
CF.sub.3 -- C.sub.2 H.sub.5 OC.sub.2 H.sub.5 (IA) logP =
3.19.sup.a) 5 CH.sub.2 O ##STR421## CN Br -- SCH.sub.3 CH.sub.3
(IA) logP = 2.83.sup.a) 6 CH.sub.2 O ##STR422## CN Br -- OC.sub.2
H.sub.5 CH.sub.3 (IA) logP = 2.94.sup.a) 7 CH.sub.2 O ##STR423## CN
F -- N(CH.sub.3).sub.2 CH.sub.3 (IA) logP = 2.28.sup.a) 8 CH.sub.2
O ##STR424## CN F -- OCH.sub.3 ##STR425## (IA) logP = 2.56.sup.a) 9
CH.sub.2 O ##STR426## CN SO.sub.2 CH.sub.3 -- SCH.sub.3 CH.sub.3
(IA) logP = 1.74.sup.a) 10 CH.sub.2 O ##STR427## CN CF.sub.3 --
CH.sub.3 CH.sub.3 (IA) logP = 2.35.sup.a)
##STR428##
TABLE 1a Examples of the compounds of the formula (I) Ex.
(position) (position) (position) Physical No. R.sup.1 R.sup.2
R.sup.3 (R.sup.4).sub.n --A--Z data ID-1 ##STR429## H (2) Cl (4) Cl
##STR430## logP = 2.34.sup.a) ID-2 ##STR431## H (2) OCH.sub.3 (4)
Cl ##STR432## ID-3 ##STR433## H (2) Cl (4) Cl ##STR434## ID-4
##STR435## H (2) OCH.sub.3 (4) Cl ##STR436## ID-5 ##STR437## H (2)
Cl (4) Cl ##STR438## ID-6 ##STR439## H (2) Cl (4) Cl ##STR440##
ID-7 ##STR441## H (2) Cl (4) Cl ##STR442## ID-8 ##STR443## H (2) Cl
(4) Cl ##STR444## ID-9 ##STR445## H (2) Cl (4) Cl ##STR446## ID-10
##STR447## H (2) OCH.sub.3 (4) Cl ##STR448## ID-11 ##STR449## H (2)
Cl (4) SO.sub.2 CH.sub.3 ##STR450## ID-12 ##STR451## H (2) Cl (4)
SO.sub.2 CH.sub.3 ##STR452## ID-13 ##STR453## H (2) SO.sub.2
CH.sub.3 (4) Cl ##STR454## ID-14 ##STR455## H (2) SO.sub.2 CH.sub.3
(4) Cl ##STR456## ID-15 ##STR457## H (2) Cl (4) CF.sub.3 ##STR458##
ID-16 ##STR459## H (2) Cl (4) CF.sub.3 ##STR460## ID-17 ##STR461##
H (2) NO.sub.2 (4) CF.sub.3 ##STR462## ID-18 ##STR463## H (2)
NO.sub.2 (4) CF.sub.3 ##STR464## ID-19 ##STR465## H (2) OCH.sub.3
(4) CF.sub.3 ##STR466## ID-20 ##STR467## H (2) OCH.sub.3 (4)
CF.sub.3 ##STR468## ID-21 ##STR469## H (2) Cl (4) CN ##STR470##
ID-22 ##STR471## H (2) Cl (4) CN ##STR472## ID-23 ##STR473## H (2)
OCH.sub.3 (4) CN ##STR474## ID-24 ##STR475## H (2) OCH.sub.3 (4) CN
##STR476## ID-25 ##STR477## H (2) Cl (4) F ##STR478## ID-26
##STR479## H (2) Cl (4) F ##STR480## ID-27 ##STR481## H H --
##STR482## ID-28 ##STR483## H H -- ##STR484## ID-29 ##STR485## H
(4) F -- ##STR486## ID-30 ##STR487## H (4) F -- ##STR488## ID-31
##STR489## H (4) Cl -- ##STR490## ID-32 ##STR491## H (4) Cl --
##STR492## ID-33 ##STR493## H (4) F -- ##STR494## ID-34 ##STR495##
H (4) Cl -- ##STR496## ID-35 ##STR497## H (4) Br -- ##STR498##
ID-36 ##STR499## H (4) I -- ##STR500## ID-37 ##STR501## H (4)
NO.sub.2 -- ##STR502## ID-38 ##STR503## H (4) CN -- ##STR504##
ID-39 ##STR505## H (4) CF.sub.3 -- ##STR506## ID-40 ##STR507## H
(4) SO.sub.2 CH.sub.3 -- ##STR508## ID-41 ##STR509## H (4)
OCH.sub.3 -- ##STR510## ID-42 ##STR511## H (4) OCF.sub.3 --
##STR512## ID-43 ##STR513## H (4) OCHF.sub.2 -- ##STR514## ID-44
##STR515## H (4) SCH.sub.3 -- ##STR516## ID-45 ##STR517## H (4)
SOCH.sub.3 -- ##STR518## ID-46 ##STR519## ##STR520## (2) Cl (4) Cl
##STR521## ID-47 ##STR522## ##STR523## (2) OCH.sub.3 (4) Cl
##STR524## ID-48 ##STR525## ##STR526## (2) Cl (4) Cl ##STR527##
ID-49 ##STR528## ##STR529## (2) OCH.sub.3 (4) Cl ##STR530## ID-50
##STR531## SCH.sub.3 (2) Cl (4) Cl ##STR532## ID-51 ##STR533##
SCH.sub.3 (2) OCH.sub.3 (4) Cl ##STR534## ID-52 ##STR535##
SCH.sub.3 (2) Cl (4) Cl ##STR536## ID-53 ##STR537## SCH.sub.3 (2)
OCH.sub.3 (4) Cl ##STR538## ID-54 ##STR539## H (2) Cl (4) Cl
##STR540## ID-55 ##STR541## H (2) OCH.sub.3 (4) Cl ##STR542## ID-56
##STR543## H (2) Cl (4) Cl ##STR544## ID-57 ##STR545## H (2)
OCH.sub.3 (4) Cl ##STR546## ID-58 ##STR547## H (4) CF.sub.3 --
##STR548## ID-59 ##STR549## H (4) CF.sub.3 -- ##STR550## ID-60
##STR551## H (4) CF.sub.3 -- ##STR552## ID-61 ##STR553## H (2) Cl
(4) Cl ##STR554## ID-62 ##STR555## H (2) OCH.sub.3 (4) Cl
##STR556## ID-63 ##STR557## H (2) Cl (4) Cl ##STR558## ID-64
##STR559## H (2) OCH.sub.3 (4) Cl ##STR560## ID-65 ##STR561## H (2)
Cl (4) Cl ##STR562## ID-66 ##STR563## H (2) OCH.sub.3 (4) Cl
##STR564## ID-67 ##STR565## H (2) NO.sub.2 (4) SO.sub.2 CH.sub.3
##STR566## ID-68 ##STR567## H (2) NO.sub.2 (4) SO.sub.2 CH.sub.3
##STR568## ID-69 ##STR569## H (2) Cl (4) SO.sub.2 CH.sub.3
##STR570## ID-70 ##STR571## H (2) NO.sub.2 (4) SO.sub.2 CH.sub.3
##STR572## ID-71 ##STR573## H (2) NO.sub.2 (4) CF.sub.3 ##STR574##
ID-72 ##STR575## H (2) NO.sub.2 (4) CF.sub.3 ##STR576## ID-73
##STR577## H (2) Cl (4) SO.sub.2 CH.sub.3 ##STR578## ID-74
##STR579## H (2) NO.sub.2 (4) SO.sub.2 CH.sub.3 ##STR580## ID-75
##STR581## H (2) NO.sub.2 (4) CF.sub.3 ##STR582## ID-76 ##STR583##
H (2) Cl (4) SO.sub.2 CH.sub.3 ##STR584## ID-77 ##STR585## H (2)
NO.sub.2 (4) SO.sub.2 CH.sub.3 ##STR586## ID-78 ##STR587## H (2)
NO.sub.2 (4) CF.sub.3 ##STR588##
The logP values given in Table 1 and 1a were determined in
accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High
Performance Liquid Chromatography) using a reverse-phase column (C
18). Temperature: 43.degree. C.
(a) Mobile phases for the determination in the acidic range: 0.1%
aqueous phosphoric acid, acetonitrile; linear gradient from 10%
acetonitrile to 90% acetonitrile--the corresponding data in Table 1
are labelled.sup.a).
(b) Mobile phases for the determination in the neutral range: 0.01
molar aqueous phosphate buffer solution, acetonitrile; linear
gradient from 10% acetonitrile to 90% acetonitrile--the
corresponding data in Table 1 are labelled.sup.b).
Calibration was carried out using unbranched alkan-2-ones (with
from 3 to 16 carbon atoms) whose logP values are known
(determination of the logP values by the retention times using
linear interpolation between two successive alkanones).
The lambda-max values were determined in the maxima of the
chromatographic signals, using the UV spectra from 200 nm to 400
nm.
Starting Materials of the Formula (II)
Example (II-1)
##STR589##
At -60.degree. C., 100 ml of a 1.6 molar solution of butyllithium
in hexane are added to 30 ml of tetrahydrofuran. At -60.degree. C.,
6.6 g (0.16 mol) of acetonitrile and 14.6 g (0.15 mol) of methyl
cyclopropanecarboxylate are then added successively. The resulting
white suspension is, after the cooling bath has been removed and
the mixture has reached room temperature, poured into about the
same amount of 2 N hydrochloric acid and then extracted three times
with methylene chloride. The organic extract solutions are
combined, dried with sodium sulphate and filtered. The solvent is
carefully distilled off from the filtrate under water pump vacuum
and the residue is distilled under relatively low pressure.
This gives 7.5 g (46% of theory) of cyanomethyl cyclopropyl ketone
of boiling point 56.degree. C. (at 0.8 mbar).
Starting Materials of the Formula (III)
Example (III-1)
##STR590##
4.5 g (15 mmol) of
2-(3-chloro-4-cyano-phenyl)-4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,2,
4-triazol-3-one are taken up in 80 ml of 60% strength sulphuric
acid, and the mixture is heated under reflux for 6 hours. After
cooling to room temperature, the resulting crystalline product is
isolated by filtration with suction. This gives 4.5 g (91% of
theory) of
2-(3-carboxy-4-chloro-phenyl)-4-methyl-5-trifluoromethyl-2,4-dihydro-3H-1,
2,4-triazol-3-one of melting point 223.degree. C.
Example (III-2)
##STR591##
2 g (4.9 mmol) of
5-bromo-4-methyl-2-(2-ethoxycarbonyl-5-trifluoromethyl-benzyl)-2,4-dihydro
-3H-1,2,4-triazol-3-one (cf. Example IV-1) are dissolved in 30 ml
of 10% strength ethanolic potassium hydroxide solution, and the
mixture is heated under reflux for 2 hours. The reaction mixture is
concentrated under water pump vacuum, taken up in 20 ml of water
and acidified using dilute hydrochloric acid. The solid that
precipitates out is filtered off and dried.
This gives 1.2 g (71% of theory) of
5-ethoxy-4-methyl-2-(2-carboxy-5-trifluoromethyl-benzyl)-2,4-dihydro-3H-1,
2,4-triazol-3-one as a solid product.
logP: 2.18.sup.a)
Example (III-3)
##STR592##
13.4 g (35 mmol) of
4-methyl-5-trifluoromethyl-2-(2,6-dichloro-3-methoxycarbonyl-benzyl)-2,4-d
ihydro-3H-1,2,4-triazol-3-one are initially charged in 60 ml of
1,4-dioxane, and a solution of 1.54 g (38.5 mmol) of sodium
hydroxide in 20 ml of water is slowly metered in at room
temperature. The reaction mixture is stirred at 60.degree. C. for
150 minutes and then concentrated under water pump vacuum. The
residue is dissolved in 100 ml of water, and the pH of the solution
is adjusted to 1 by addition of conc. hydrochloric acid. The
resulting crystalline product is isolated by filtration with
suction.
This gives 11.7 g (90% of theory) of
4-methyl-5-trifluoromethyl-2-(2,6-dichloro-3-carboxy-benzyl)-2,4-dihydro-3
H-1,2,4-triazol-3-one of melting point 207.degree. C.
Analogously to Examples (III-1) to (III-3), it is also possible to
prepare, for example, the compounds of the general formula (m)
listed in Table 2 below. ##STR593##
TABLE 2 Examples of the compounds of the formula (III) Ex.
(position-) (position-) (position-) Physical No. R.sup.3
(R.sup.4).sub.n -A-Z data III-4 (4-) Cl -- ##STR594## logP =
1.39.sup.a) III-5 (4-) SO.sub.2 CH.sub.3 -- ##STR595## logP =
1.47.sup.a) III-6 (4-) F -- ##STR596## logP = 1.73.sup.a) III-7
(4-) CF.sub.3 -- ##STR597## logP = 1.65.sup.a) III-8 (4-) Br --
##STR598## logP = 1.74.sup.a) III-9 (4-) CF.sub.3 -- ##STR599##
logP = 2.43.sup.a) III-10 (4-) CF.sub.3 -- ##STR600## logP =
2.12.sup.a) III-11 (4-) CF.sub.3 -- ##STR601## logP = 1.61.sup.a)
III-12 (4-) CF.sub.3 -- ##STR602## logP = 1.93.sup.a) III-13 (4-)
CF.sub.3 -- ##STR603## logP = 2.01.sup.a) III-14 (4-) CF.sub.3 --
##STR604## logP = 1.77.sup.a) III-15 (3-) CH.sub.3 -- ##STR605##
logP = 1.70.sup.a) III-16 (4-) SO.sub.2 CH.sub.3 -- ##STR606## logP
= 1.07.sup.a) III-17 (4-) CF.sub.3 -- ##STR607## logP = 2.35.sup.a)
III-18 (4-) CF.sub.3 -- ##STR608## logP = 2.63.sup.a) III-19 (4-)
CF.sub.3 -- ##STR609## logP = 2.13.sup.a) III-20 (4-) CF.sub.3 --
##STR610## logP = 1.82.sup.a) III-21 (4-) CF.sub.3 -- ##STR611##
logP = 2.48.sup.a) III-22 (4-) CF.sub.3 -- ##STR612## logP =
1.73.sup.a) III-23 (4-) CF.sub.3 -- ##STR613## logP = 3.11.sup.a)
III-24 (4-) F -- ##STR614## logP = 1.43.sup.a) III-25 (4-) F --
##STR615## logP = 1.97.sup.a) III-26 (4-) F -- ##STR616## logP =
1.30.sup.a) III-27 (4-) F -- ##STR617## logP = 1.63.sup.a) III-28
(4-) F -- ##STR618## logP = 1.93.sup.a) III-29 (4-) CF.sub.3 --
##STR619## logP = 1.78.sup.a) III-30 (2-) Cl (4-) Cl ##STR620##
m.p.: 230.degree. C. logP = 1.63.sup.a) III-31 (2-) Cl (4-) Cl
##STR621## m.p.: 190.degree. C. logP = 1.73.sup.a) III-32 (2-) Cl
(4-) Cl ##STR622## m.p.: 210.degree. C. logP = 1.87.sup.a) III-33
(2-) Cl (4-) Cl ##STR623## m.p.: 210.degree. C. logP = 1.43.sup.a)
III-34 (2-) Cl (4-) Cl ##STR624## m.p.: 164.degree. C. logP =
2.01.sup.a) III-35 (2-) Cl (4-) Cl ##STR625## m.p.: 168.degree. C.
logP = 2.04.sup.a) III-36 (2-) Cl (4-) Cl ##STR626## m.p.:
218.degree. C. logP =1.53.sup.a) III-37 (2-) Cl (4-) Cl ##STR627##
m.p.: 259.degree. C. logP = 0.98.sup.a) III-38 (2-) Cl (4-) Cl
##STR628## m.p.: 210.degree. C. logP =1.56.sup.a) III-39 (2-) Cl
(4-) Cl ##STR629## m.p.: 197.degree. C. logP = 1.51.sup.a) III-40
(2-) Cl (4-) Cl ##STR630## m.p.: 262.degree. C. logP = 1.11.sup.a)
III-41 (2-) Cl (4-) Cl ##STR631## m.p.: 249.degree. C. logP =
1.30.sup.a) III-42 (2-) Cl (4-) Cl ##STR632## m.p.: 200.degree. C.
logP = 1.71.sup.a) III-43 (2-) Cl (4-) Cl ##STR633## m.p.:
189.degree. C. logP = 2.01.sup.a) III-44 (2-) Cl (4-) Cl ##STR634##
m.p.: 178.degree. C. logP = 2.28.sup.a) III-45 (2-) Cl (4-) Cl
##STR635## m.p.: 161.degree. C. logP = 2.31.sup.a) III-46 (2-) Cl
(4-) Cl ##STR636## m.p.: 200.degree. C. logP = 1.98.sup.a) III-47
(2-) Cl (4-) Cl ##STR637## m.p.: 201.degree. C. logP = 1.39.sup.a)
III-48 (2-) Cl (4-) Cl ##STR638## m.p.: 207.degree. C. logP =
1.77.sup.a) III-49 (2-) Cl (4-) Cl ##STR639## m.p.: 140.degree. C.
logP = 1.88.sup.a) III-50 (4-) OCH.sub.2 CHF.sub.2 -- ##STR640##
m.p.: 154.degree. C. logP = 2.14.sup.a) III-51 -- -- ##STR641##
m.p.: 214.degree. C. logP = 1.87.sup.a) III-52 -- -- ##STR642##
m.p.: 194.degree. C. logP = 2.07.sup.a) III-53 -- -- ##STR643##
m.p.: 181.degree. C. logP = 1.97.sup.a) III-54 -- -- ##STR644##
m.p.: 251.degree. C. logP = 1.14.sup.a) III-55 (2-) Cl (4-) Cl
##STR645## logP = 1.38.sup.a) III-56 (2-) Cl (4-) Cl ##STR646##
logP = 1.48.sup.a) III-57 (2-) Cl (4-) Cl ##STR647## IlI-58 (4-) Cl
-- ##STR648## .sup.1 H-NMR (DMSO-D6, .delta.): 5.42 ppm. III-59
(4-) CF.sub.3 -- ##STR649## .sup.1 H-NMR (DMSO-D6, .delta.): 5.48
ppm. III-60 (4-) CF.sub.3 -- ##STR650## .sup.1 H-NMR (DMSO-D6,
.delta.): 5.60 ppm. logP = 2.47.sup.a) III-61 (4-) CF.sub.3 --
##STR651## logP = 2.33.sup.a) III-62 (4-) SO.sub.2 CH.sub.3 --
##STR652## .sup.1 H-NMR (DMSO-D6, .delta.): 5.14 ppm. III-63 (4-)
SO.sub.2 CH.sub.3 -- ##STR653## .sup.1 H-NMR (DMSO-D6, .delta.):
5.27 ppm. III-64 (4-) Cl -- ##STR654## .sup.1 H-NMR (CDCl.sub.3,
.delta.): 5.12 ppm. III-65 (4-) Cl -- ##STR655## .sup.1 H-NMR
(DMSO-D6, .delta.): 5.20 ppm. III-66 (4-) Cl -- ##STR656## .sup.1
H-NMR (DMSO-D6, .delta.): 5.03 ppm. III-67 (4-) Br -- ##STR657##
.sup.1 H-NMR (DMSO-D6, .delta.): 5.24 ppm. III-68 (4-) Br --
##STR658## .sup.1 H-NMR (DMSO-D6, .delta.): 5.39 ppm. III-69 (4-) F
-- ##STR659## .sup.1 H-NMR (DMSO-D6, .delta.): 5.19 ppm. III-70
(4-) F -- ##STR660## .sup.1 H-NMR (DMSO-D6, .delta.): 5.30 ppm.
III-71 (4-) F -- ##STR661## .sup.1 H-NMR (DMSO-D6, .delta.): 5.43
ppm. III-72 (4-) Br -- ##STR662## .sup.1 H-NMR (CDCl.sub.3
.delta.): 5.10 ppm. III-73 (4-) Br -- ##STR663## .sup.1 H-NMR
(DMSO-D6, .delta.): 5.03 ppm. III-74 (4-) Br -- ##STR664## .sup.1
H-NMR (DMSO-D6, .delta.): 5.19 ppm. III-75 (4-) Br -- ##STR665##
.sup.1 H-NMR (DMSO-D6, .delta.): 5.01 ppm. III-76 (4-) Cl --
##STR666## .sup.1 H-NMR (DMSO-D6, .delta.): 5.14 ppm. III-77 (4-)
Cl -- ##STR667## .sup.1 H-NMR (DMSO-D6, .delta.): 5.25 ppm. III-78
(4-) NO.sub.2 -- ##STR668## .sup.1 H-NMR (DMSO-D6, .delta.): 5.23
ppm. III-79 (4-) NO.sub.2 -- ##STR669## .sup.1 H-NMR (DMSO-D6,
.delta.): 5.37 ppm. III-80 (4-) CF.sub.3 -- ##STR670## logP =
2.46.sup.a) III-81 (4-) CF.sub.3 -- ##STR671## .sup.1 H-NMR
(DMSO-D6, .delta.): 5.31 ppm. III-82 (4-) CF.sub.3 -- ##STR672##
logP = 2.08.sup.a) III-83 (4-) OCH.sub.3 -- ##STR673## .sup.1 H-NMR
(CDCl.sub.3, .delta.): 5.38 ppm. III-84 (4-) OCH.sub.3 --
##STR674## .sup.1 H-NMR (CDCl.sub.3, .delta.): 5.43 ppm. III-85
(4-) CF.sub.3 -- ##STR675## .sup.1 H-NMR (CDCl.sub.3, .delta.):
5.47 ppm. III-86 (4-) Br -- ##STR676## logP = 1.44.sup.a) III-87
(4-) Br -- ##STR677## logP = 1.63.sup.a) III-88 (4-) Br --
##STR678## logP = 2.27.sup.a) III-89 (4-) Br -- ##STR679## logP =
2.31.sup.a) III-90 -- -- ##STR680## logP = 1.82.sup.a) III-91 (4-)
Br -- ##STR681## .sup.1 H-NMR (CDCl.sub.3, .delta.): 5.32 ppm.
III-92 (4-) Br -- ##STR682## .sup.1 H-NMR (CDCl.sub.3, .delta.):
5.53 ppm. III-93 (4-) F -- ##STR683## .sup.1 H-NMR (CDCl.sub.3,
.delta.): 5.39 ppm. III-94 (4-) F -- ##STR684## .sup.1 H-NMR
(CDCl.sub.3, .delta.): 5.57 ppm. III-95 (4-) F -- ##STR685## .sup.1
H-NMR (CDCl.sub.3, .delta.): 5.44 ppm. III-96 (4-) F -- ##STR686##
.sup.1 H-NMR (CDCl.sub.3, .delta.): 5.41 ppm. III-97 -- --
##STR687## .sup.1 H-NMR (CDCl.sub.3, .delta.): 5.34 ppm. III-98 --
-- ##STR688## .sup.1 H-NMR (CDCl.sub.3, .delta.): 5.38 ppm. III-99
-- -- ##STR689## .sup.1 H-NMR (CDCl.sub.3, .delta.): 5.26 ppm.
III-100 -- -- ##STR690## .sup.1 H-NMR (CDCl.sub.3, .delta.): 5.43
ppm. III-101 -- -- ##STR691## logP = 1.23.sup.a) III-102 (4-)
SO.sub.2 CH.sub.3 -- ##STR692## logP = 1.14.sup.a) III-103 (4-)
CF.sub.3 -- ##STR693## logP = 2.45.sup.a) III-104 (4-) CF.sub.3 --
##STR694## logP = 2.48.sup.a) III-105 (4-) Br -- ##STR695## logP =
1.85.sup.a) III-106 (4-) CF.sub.3 -- ##STR696## logP = 2.74.sup.a)
III-107 (4-) CF.sub.3 -- ##STR697## logP = 2.01.sup.a) III-108 (4-)
CF.sub.3 -- ##STR698## logP = 1.79.sup.a) III-109 (4-) CF.sub.3 --
##STR699## logP = 1.65.sup.a) III-110 (4-) Br -- ##STR700## logP=
1.90.sup.a) III-111 (4-) Cl -- ##STR701## logP = 1.83.sup.a)
III-112 (4-) I -- ##STR702## logP = 2.06.sup.a) III-113 (4-) I --
##STR703## m.p.: 104.degree. C. logP = 2.39.sup.a) III-114 (4-) Br
-- ##STR704## m.p.: 191.degree. C. III-115 (4-) Br -- ##STR705##
m.p.: 213.degree. C. III-116 -- -- ##STR706## III-117 -- --
##STR707## m.p.: 112.degree. C. III-118 (4-) CF.sub.3 -- ##STR708##
m.p.: 158.degree. C. III-119 (4-) CF.sub.3 -- ##STR709## m.p.:
162.degree. C. III-120 (4-) Cl (5-) Cl ##STR710## m.p.: 167.degree.
C. III-121 -- -- ##STR711## m.p.: 188.degree. C. III-122 -- --
##STR712## III-123 -- -- ##STR713## m.p.: 131.degree. C. III-124
(4-) Cl -- ##STR714## m.p.: 109.degree. C. III-125 (4-) I --
##STR715## m.p.: 104.degree. C. III-126 (4-) Br -- ##STR716## m.p.:
99.degree. C. III-127 (4-) Br -- ##STR717## m.p.: 174.degree. C.
III-128 -- -- ##STR718## m.p.: 122.degree. C.
III-129 (4-) Br -- ##STR719## m.p.: 164.degree. C. III-130 -- --
##STR720## m.p.: 154.degree. C. III-131 (4-) Br -- ##STR721## m.p.:
161.degree. C. III-132 (4-) CN -- ##STR722## m.p.: 196.degree. C.
III-133 -- -- ##STR723## m.p.: 192.degree. C. III-134 -- --
##STR724##
The logP values given in Table 2 were determined in accordance with
EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid
Chromatography) using a reverse-phase column (C 18). Temperature:
43.degree. C.
(a) Mobile phases for the determination in the acidic range: 0.1%
aqueous phosphoric acid, acetonitrile; linear gradient from 10%
acetonitrile to 90% acetonitrile--the corresponding data in Table 2
are labelled.sup.a).
(b) Mobile phases for the determination in the neutral range: 0.01
molar aqueous phosphate buffer solution, acetonitrile; linear
gradient from 10% acetonitrile to 90% acetonitrile--the
corresponding data in Table 2 are labelled.sup.b).
Calibration was carried out using unbranched alkan-2-ones (with
from 3 to 16 carbon atoms) whose logP values are known
(determination of the logP values by the retention times using
linear interpolation between two successive alkanones).
The lambda-max values were determined in the maxima of the
chromatographic signals, using the UV spectra from 200 nm to 400
nm.
Starting Materials of the Formula (IV)
Example (IV-1)
##STR725##
At room temperature (about 20.degree. C.), a solution of 1.20 g
(33% strength, i.e. 2.8 mmol) of methyl
4-(3-bromomethyl-5-trifluoromethyl-benzoyl)-5-cyclopropyl-isoxazole-3-carb
oxylate in 10 ml of N,N-dimethyl-formamide is added dropwise with
stirring to a mixture of 0.44 g (2.8 mmol) of
4-ethoxy-5-ethyl-2,4-dihydro-3H-1,2,4-triazol-3-one, 84 mg (2.8
mmol) of sodium hydride (75% strength) and 20 ml of
N,N-dimethyl-formamide, and the reaction mixture is stirred at room
temperature for 30 minutes. The mixture is subsequently diluted
with saturated aqueous sodium chloride solution to about twice its
volume and extracted twice with ethyl acetate. The combined organic
extract solutions are dried with sodium sulphate and filtered. The
filtrate is concentrated under water pump vacuum and the residue is
purified by column chromatography (silica gel, hexane/ethyl
acetate, vol.: 7/3).
This gives 0.45 g (96% of theory based on 33% strength starting
material) of
(5-cyclopropyl-3-methoxycarbonyl-isoxazol-4-yl)-[2-(4-ethoxy-3-ethyl-5-oxo
-4,5-dihydro-[
1,2,4]-triazol-1-yl-methyl)-4-trifluoromethyl-phenyl]-methanone as
an amorphous product.
logP (determined at pH=2.3): 3.56.
USES EXAMPLES
Example A
Pre-emergence Test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by
weight of active compound is mixed with the stated amount of
solvent, the stated amount of emulsifier is added and the
concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24
hours, the soil is sprayed with the preparation of active compound
such that the particuiar amount of active compound desired is
applied per unit area. The concentration of the spray liquor is
chosen so that the particular amount of active compound desired is
applied in 1000 litres of water per hectare.
After three weeks, the degree of damage to the plants is rated in %
damage in comparison to the development of the untreated
control.
The figures denote:
0%=no effect (like untreated control)
100%=total destruction
In this test, for example, the compounds of Preparation Examples 1,
2, 3, 4, 5 and 6 exhibit strong activity against weeds, whilst
being tolerated well by crop plants, such as, for example,
maize.
Example B
Post-emergence Test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by
weight of active compound is mixed with the stated amount of
solvent, the stated amount of emulsifier is added and the
concentrate is diluted with water to the desired concentration.
Test plants of a height of 5 to 15 cm are sprayed with the
preparation of active compound such that the particular amounts of
active compound desired are applied per unit area. The
concentration of the spray liquor is chosen so that the particular
amounts of active compound are applied in 1000 l of water/ha.
After three weeks, the degree of damage to the plants is rated in %
damage in comparison to the development of the untreated
control.
The figures denote:
0%=no effect (like untreated control)
100%=total destruction
In this test, for example, the compounds of Preparation Examples 1,
2, 3, 4, 5 and 6 exhibit strong activity against weeds, and some of
them are tolerated well by crop plants, such as, for example,
maize.
* * * * *